DE3012360C2 - Photothermoplastic recording process for optical information and recording material for carrying out this process - Google Patents

Description

to octyl methacrylate 30-50

Vinylphenylamine 5-15

Halostyrene 35-65

20. Recording material according to claim 17, characterized in that the thermoplastic storage layer is made from a terpolymer made from the following monomer components (in mol%):

Octyl methacrylate 30-35

Vmylphenyl isothiocyanate 5-10

Halostyrene 35-60

21. Recording material according to any one of claims 2 to 20, characterized in that it a flexible support based on polyethylene terephthalate in a proportion of 0.05 to 0.5 part by weight of 1,1-diacetylferrocene.

The invention relates to a photothermoplastic recording method according to the preamble of the claim 1 and recording materials for carrying out such processes.

The invention can be used in the field of photo and cinema technology.

Various photothermoplastic optical information recording methods are known. For example, US-PS 28 33 648 describes a method in which on a photoconductive layer in conventional Manner, an electrostatic latent image is formed. The photoconductive layer with the latent electrostatic image is then brought into contact with a dielectric thermoplastic layer which was previously charged opposite to the photoconductive layer by means of a corona discharge. After Charge transfer, the layers are separated from each other, and when the size of the air gap becomes one approaches a critical value, an electrical breakdown occurs in the area of the figure, which turns out to be Transfer of the electrostatic image to the dielectric thermoplastic layer expresses the various Variations of this procedure, e.g. B. in US-PS 29 37 943 or 30 55 006 are described as Charge image transfer process referred to over an air gap. However, in such procedures obtained mirror images on the thermoplastic layer. It is also difficult to keep the gap width across the entire keep exposed area constant. Furthermore, the resolution decreases with increasing slit width, and there is considerable fogging.

To reduce fogging, neutralization is carried out after an electrostatic image has formed the charges on the background image areas by charging with an opposite sign, See U.S. Patent 3,196,011.

Another recording method using a thermoplastic photoconductive material according to US-PS 32 83 309 and 33 60 784 one is applied to a transparent conductive layer support transparent photoconductive layer with thermoplastic properties charged and imagewise exposed. Thereafter, the recording material is heated to its flow temperature, so that the picture elements having sections are deformed and the image develops in the form of a visible relief. By The image is fixed when it is cooled to room temperature.

Because in this process both photoconductivity and thermoplastic within a single layer Properties must be present, the photosensitivity is low. Furthermore, because of the instability of the photoconductive layers only a few working cycles possible, there is a considerable edge effect in the Deformation at the border of light and shadow, and halftone transfer is an additional one Screening of the projected image required.

In other optical information recording materials, recording materials are used which have a photoconductive layer and a thermoplastic memory layer disclosed in US Pat Sequence are arranged one above the other on an electrically conductive layer support.

Such processes are described in US Pat. Nos. 3,196,008 and 3,560,206. In these procedures, the Free surface of the thermoplastic layer is evenly charged electrostatically. Then this surface becomes imagewise exposed to light to which the photoconductive layer is responsive. Under the influence of this Exposure forms a spatially modulated potential relief that corresponds to the original either to be developed immediately, or to be developed after a uniform recharge carried out For development, the thermoplastic layer is quickly heated to a temperature that corresponds to its Flow temperature briefly exceeded Under the effect of electrostatic forces (pondcromolorischcr Forces: electrostatic forces per unit area) creates a roughness pattern that is spatially modulated

Corresponds to potential relief.

The main disadvantage of such a process with the steps of charging, exposure and development is that it is long Duration of the process, the low photosensitivity due to a high degree of dark relaxation with discharge of charge before softening of the thermoplastic recording layer and a low signal-to-noise ratio as a result of deformations in unexposed portions of the thermoplastic layer.

To increase the photosensitivity, the thermoplastic layer is applied directly before the exposure after the exposure Development charged additionally. This increases the sensitivity, but also the noise. Without Avoiding the other disadvantages mentioned also increases the total time of the recording process.

The implementation of loading and Umladc-steps in the context of a process management, which we in kung of electrostatic forces on a surface section for such a period ensures that in form this section as a result of the deformation of the thermoplastic layer ice bloom pattern (see. US-PS 31 96 011 and GB-PS 1049 881), enables the edge effect to be eliminated. The obtained moiré patterns allow large-area sections of constant illuminance in optical images with a constant Background to reproduce analogous to photography with silver halide recording materials without however, that the process is relieved of the remaining disadvantages.

To increase the signal-to-noise ratio, in the known recording method additional work steps for uniform exposure of the photosensitive layer after a previous one Charge, for recharging after the uniform exposure with the same sign as the previous one Charging, as well as recharging to a potential with the opposite sign after exposure and performed right before development.

A large number of working steps during the recording process require recording devices of complicated design and recording materials in which the specific resistances of the thermoplastic layer and the photoconductive layer have to meet increased requirements. ^{Specific resistances in the range from 10 μ} to 10 ¹⁵ ohm · cm are to be regarded as the lower limit for recording materials which can be used in practice for step-by-step recording, in particular with additional steps for charging and recharging. To eliminate the edge effects that increase the conductivity of the layers, greater layer thicknesses are used, which reduce the boundary resolution, but do not allow the use of inorganic photoconductors on a flexible layer carrier. These high resistance values and the absence of leakage currents require a capacitive equivalent circuit of the recording material. At the moment of exposure, the capacitor corresponding to an illuminated area of the photoconductive layer is short-circuited. Such a conception of the recording material corresponds only to a rough approximation and does not allow a characterization of optimal recording conditions.

A common disadvantage of all known recording methods described is that there are no statements the relationship between the critical values for a recording process, the charge potential, Duration of charging, exposure, reloading and developing with the parameters of the recording material make forming layers. Without knowledge of such relationships, it is impossible to achieve optimal results To achieve recording conditions where maximum sensitivity, a large signal-to-noise ratio and ensures the required values for the contrast factor and the exposure latitude are.

From GB-PS 11 81 093 a method is known in which the known steps are carried out to form a roughness image, and in which a correlation of the parameters of a first charge with those of the recharge after the exposure is established in order to obtain the required values for to get the contrast factor. In this method, a recording material is used which has an electrically conductive layer support, a photoconductive layer arranged thereon with a thickness d _s and an absolute dielectric constant e "s _s as well as a thermoplastic storage layer with a thickness d _p and an absolute dielectric constant ε, _ρ includes. This recording material is charged to a first potential V ", then exposed in such a way that the potential in the bcleuchietcn sections drops to a value Vf and is then charged again to a potential V" (recharge potential), a distribution of the surface charges oru according to the gives the following expression:

Ore = Cc

that the value is sufficiently large am- so that a preceding given value of the contrast factor after formation of the Rauhigkeitsbildes is obtained as a result of deformation of the thermoplastic layer at a rapid development are selected in the V 'and V "in such a way.

In order to obtain low values for the contrast factor, the recording material is first switched to a relative low initial potential, while a higher voltage is applied for recharging according to the above equation is sufficient for the required increase in the contrast factor.

In order to obtain higher values for the contrast factor, relatively high potentials are used for the first Charging and corresponding potentials applied for recharging.

The procedure described is based on two assumptions:

1. In the case of any formation of a roughness pattern, a certain one must already be formed before it is formed The minimum value for the charge density must be reached;

2. There is a certain maximum value for the charge density, above which the density of the roughness image no longer increases appreciably.

Disregarding leakage currents in the known method for creating a recording material very high-resistance materials for the photoconductive layer and the thermoplastic storage layer proposed, as well as working at relatively low electric field strengths that are not are able to generate leakage currents to a significant extent.

The known method described, in which leakage currents and associated dark potential drops on the thermoplastic storage layer and the photoconductive layer are excluded, does not contain any technical teaching for the correlation of the charge time. Exposure time. Recharge time and heating time, which is why this process cannot be carried out using recording materials that have thin photoconductive layers and thermoplastic storage layers, in particular those made of materials with relatively low resistivities (below 10 ^{1 J} ohm · cm).

In order to carry out the optical information recording method, a recording material used with a deformable dielectric layer in which the image appears as disordered bumps and forming pits equidistant from each other in a zone 1 to 5 times larger than that Layer thickness, the distance from the top to the bottom of the size of the electrostatic forces depend. The recording material used consists of a support with an electrical conductive coating as well as a photoconductive layer and a thermoplastic storage layer made of high-resistance Materials together.

As in the case of conventional electrophotographic recording materials, the substrate is made of metal, for example made of aluminum or brass or of glass with an electrically conductive coating. It is known per se to use flexible materials as support for recording materials, for example silica-containing polyethylene terephthalate (US-PS 35 47 644), cellulose triacetate (US-PS 35 51 152) or polyethylene terephthalate (SU Inventor's Certificate No. 4 79 146).

The use of these flexible materials for recording materials, which have a thermoplastic storage layer and a photoconductive layer made of an inorganic photoconductor material, is a hindrance to the creation of recording materials of unlimited length, since such flexible substrates already soften ^{at slightly elevated temperatures of approx. 60 to 80 ° C} and exhibit considerable transverse and longitudinal shrinkage, which leads to a deterioration in image quality.

To carry out the known recording process, the photoconductive layer of the recording material can consist of one of the customary photoconductive materials, for example amorphous selenium, Se-As-. Se-Te mixtures, arsenic trisulfide-arsenic triselenide, with the proviso that layers with a specific resistance of more than 10 ¹⁴ ohm · cm at the recording temperature can be obtained from them.

It's cheaper. Layers of materials mostly used to manufacture storage disks for Vidikone - arsenic triselenide with additions of SbiSj, Sb ₂ Sc ₁ and heterostructures based on these and A ⁿ B ^vl compounds - to be used.

The vitreous selenium with a quantum yield close to 1 and with one compared to other materials due to slamming wider range of spectral sensitivity indicates good photosensitivity on, but crystallizes out intensively when heated and as a result changes its properties, i. H. it ages. This property makes it unsuitable for continuous storage and multiple record transmission. All other materials have a much lower Quanlenausbeule than Se, which is the duration and the Photoelectric signal factor decreased.

The thermoplastic storage layer is usually produced from polymers, for example from styrene-butyl methacrylate copolymers (US-PS 31 18 776) with the following monomer ratio (mol%):

Styrene 30 to 60

Butyl methacrylate 40 to 70.

However, such recording materials have no high processing, recording and information acquisition speed, namely, the flow is determined by the temperatures of the thermoplastic memory layer due to the high, over 100 ⁰ C lying recording temperature. The high temperatures in turn require development equipment with increased power consumption. As a result of the relatively long cooling process in the successive processes of charging, exposure and development, the high flow temperatures prevent rapid development and fixing of the recorded information, and they reduce the photosensitivity of the recording material during the simultaneous processes of charging, exposure and development thermal extinction of the photoconductivity of the photoconductive layer occurs

It is known that the temperature of the development of a generated on a thermoplastic layer electrostatic image is close to the flow temperature of the thermoplastic material, which is why high ( Values of these flow temperature development devices with increased power consumption require what we efficiency of such recording devices reduced. The heating of the thermoplastic storage layer to high development temperatures and their cooling to freezing temperatures require longer periods of time me, which slows down the registration speed and the speed of information acquisition.

Most for multilayer recording materials for photothermoplastic recording processes Photoconductive materials used show a lower photo sensitivity with increasing temperature therefore, high flow temperatures of the thermoplastic resin lead to a decrease in the total photo temp sensitivity of such recording materials leads.

According to US-PS 31 18 766 to record optical information only high-resistance thermc plastic materials are used that store high potential values over a longer period of time

can, because only high-resistance materials can be charged to potentials above 300 V and are for Recording, while materials that can only be charged to values below 300 V are suitable for the Generation of Moirc roughness patterns not suitable. This limitation is related to the thermoplastic materials to meet requirements, an electrostatic charge even in softened To be able to save the state, and that narrows the circle of those suitable for thermoplastic recording thermoplastic materials considerably. At the same time, there is a high degree of purity of the starting products and great care is required in the manufacture of the recording materials, which increases their cost and which prevents additives from being introduced into the thermoplastic storage layer, which would reduce its thermomechanical properties Properties and their adhesiveness change, as the vast majority of such additives are specific Reduces the resistance of thermoplastic materials.

As with conventional electrophotographic recording processes, the recording material is on a potential charged, which is proportional to the ratio of their capacities per unit area to the photoconductive and distributed the thermoplastic layer. The greater part of the potential comes to the photoconductive layer because it has a higher dielectric constant than the thermoplastic layer has a greater thickness and is characterized by a lower capacitance per unit area is. When exposed, the photoconductive layer becomes electrically conductive and enables the at the border Charges located between the photoconductive layer and the substrate move in the direction of the interfaces to move to the layer of thermoplastic material.

With a temporary softening of the thermoplastic material, the electrostatic deform Forces on the surface of this thermoplastic material with the formation of an ice flower-like roughness pattern with a deformation depth that corresponds to the amount of exposure captured by the various image areas is equivalent to.

The specifics of a recording material for a recording with the formation of Ice flower-like roughness images as well as the high specific resistances of the photoconductive and the thermoplastic layers make it possible to carry out the recording step by step, adding a separate Recording with charge transport from the photoconductive layer to the thermoplastic layer occurs when the steps of charging, exposure and development are separated in time. Such recording materials, however, have a considerable capacity for storing charges on what prevents rapid repetition of the recording on the same material, the circle of useful photoconductive materials to the field of conventional electrophotographic materials limited, greater thicknesses of the inorganic photoconductive layers (20 μηι) requires, which in turn Prevents training on a flexible substrate.

The ice flower-like roughness image is created on both exposed and unexposed areas of the Formed recording material, which of course the quality of the images obtained as a result of a low signal-to-noise ratio deteriorates.

The large specific resistances used to form an ice flower-like roughness pattern Layers lead to a slow charge redistribution during exposure. The optimal recording conditions are therefore long times that lie between the start of exposure and development (e.g. Recording at low illuminance levels and long exposure times). Since in such systems the The law of mutual interchangeability does not apply if there is a transition to low exposure times the folosensitivity of the recording process drops sharply with the formation of ice flower patterns. That it practically completely prevents a recording material of the known type described and a corresponding one Use the capture method for snapshots. In addition, the long ones make it difficult Times required for charge redistribution, the creation of devices for recording a movable recording material.

The formation of ice flower-like roughness images takes place at development temperatures that a Allow softening of the thermoplastic layer above its flow temperature. Hence development must as quickly as possible so as not to restore an electrostatic image that forms during heating to swing. The high development temperatures require rapid cooling so that it does not the image is erased due to surface tension.

In the known method, only a correlation between the contrast factor and the values of the Charging potentials established, but no correlation between other parameters of the recording process and the characteristics for the recording material used, which optimizes the recording conditions prevented.

The invention is based on the object of developing a photothermoplatic recording method in such a way that that it is possible to produce halftone images without special additional screening and at the same time have a large signal-to-noise ratio and to obtain short exposure times as well as a recording material for implementation to create this procedure.

These objects are achieved by a recording method according to the characterizing part of the claim 1 as well as by recording materials as described in the characterizing part of patent claims 2 and 3 are described. Advantageous configurations of the invention are specified in the subclaims.

The use of a photoconductive layer according to claim 4 enables the spectral sensitivity to move into the area of longer waves.

The use of a photoconductive layer according to claim 5 allows the range of the spectral To expand the sensitivity of the recording material.

The use of a photoconductive layer of selenium of the monoclinic modification enables one Increase in the photosensitivity of the recording material.

It is also possible to use foil-conductive materials for the production of the recording materials according to the invention

Amorphous gallium chalcogenide layers using gallium trisulfide, gallium triselenide and to use their solid solutions.

The photoconductive layer can be produced particularly advantageously from Ga2.Sj or Ga ₂ Sci. It is also desirable to produce the photoconductive layer from an inorganic folicite-capable material with a persistent conductivity.

It is also advantageous to build up the photoconductive layer in two layers, the materials of the individual layers each having a specific resistance of less than 10 "ohm-cm and the effective total resistivity of the photoconductive layer being 10" and 10 ¹² ohm-cm.

In the case of the recording materials according to the invention, it is also possible to use the functional possibilities

to a thermoplastic storage layer based on copolymers of vinyl aromatic hydrocarbons expand with alkyl methacrylate in that the thermoplastic storage shaft is made of a terpolymer from a vinyl aromatic hydrocarbon, an alkyl methacrylate and a third component Styrene derivative with a chemically active residue, which is an isocyanate group. an amino group or an isothiocyanate group can be, there is, wherein the styrene derivative with said chemically active radical in one Amount of 2 to 10 mol% of the terpolymer is present.

Preferred recording materials of this type are described in subclaims 10 to 16. A recording material according to claim 11 enables the storage time to be extended recorded information without deteriorating its quality. With the recording material according to Claim 12 is the flow temperature of the thermoplastic layer is lowered, which accelerates the Recording process and an increase in the sensitivity of the recording material allows.

The sensitivity of the recording material increases with a simultaneous increase in mechanical strength the thermoplastic layer is improved if the recording material has a thermoplastic storage layer of a terpolymer as defined in claim 17.

A recording material according to claim 13 has an extended exposure latitude, in particular when octylmeihacrylat is used as the alkyl methacrylate.

The work with the recording material according to the invention is further facilitated if one Layer support according to claim 2t used. Such a flexible layer support has an opposite known one flexible layer supports increased thermal shock resistance and elasticity.

Further tasks will become apparent to those skilled in the art from the following description of exemplary embodiments with reference to a drawing, in which the area of a recording material after recording an optical information is shown.

The photothermoplastic recording method of the present invention is based on simultaneous execution the charging and imagewise exposure of a preheated recording material, this Recording material has a substrate with an applied electrically conductive coating, a photoconductive one Layer and a thermoplastic storage layer with those recited in the claims Features included.

The electrophysical and thermomechanical parameters of the layers of the recording material determine the procedural implementation of the recording (choice of illuminance, exposure time, Charging time and the potential of the spray electrode).

The process of redistribution of voltages V to the individual layers as a result of exposure of Areas of the recording material is described by a system of equations of the following type:

(1) P ^ as as at PpUp ap at

under the initial condition

4 | 0),

4 r / (/ 0) |
as dp

wobeipi.p; ii.p; f, "£ i.p the specific contradictions. mean the thicknesses or the absolute dielectric constants of the photoconductive layer (s) or the thermoplastic storage layer (p) . The index numbers d. 1 correspond to an unexposed and an exposed part of the recording material; k is the ratio of dark resistance to the resistance of the photoconductive layer in the region of maximum brightness.

The potential redistribution results in the formation of an electrostatic latent image whose Charaklerisiikum an electrostatic contrast Δ Vist. which is defined as the voltage difference between an exposed section V ₁ , ' and an unexposed section V _p ^d on the thermoplastic storage layer of the recording material according to ^ V = Kp ¹ - V /.

The recording of optical information on the thermoplastic storage layer always requires its deformation under the action of the electrostatic forces per unit area. In order to obtain a good image quality with a high signal-to-noise ratio, a maximum difference between the electrical fields of the thermoplastic storage layer on illuminated and unilluminated sections of the recording material should therefore be aimed for. The recording material intended for rapid development is made of materials with a specific resistance in the range from 10 ″ to ΙΟ ¹ * Ω · cm

produced and ensures a charge redistribution even on the unilluminated sections of ^{the recording / recording material within a time of 10 2} to 1 s. In the recording method according to the invention using a preheated recording material, the process of forming a potential relief is accompanied by a simultaneous deformation of the surface of the thermoplastic storage layer. The maximum value of the signal-to-noise ratio is reached in this case with the charging device operating at a point in time at which the difference between the voltage drops on the thermoplastic storage layer on unexposed and exposed sections reaches a maximum value.

The solution of the system of equations (1) makes it possible to investigate the kinetics of the formation of an electrostatic contrast AV {2) as a function of the ratio of the parameters of the layers forming the recording material is described as follows:

-C ₅ PJ

When using low-resistance photoconductive layers, i.e. if / λ ¹ '< p ^ and that is at least one order of magnitude smaller, the expression (3) can be rewritten in the following form:

Λ. « -Ar In k, (4)

where r is the dark relaxation time of a charge on the recording material.

From the expression (3) it follows that for a shortening of the exposure time, i. H. for an increase in Speed of the formation of the electrostatic contrast lower resistance photoconductive layers and / or larger values for the ratio of dark resistance to resistance of the photoconductive layer are to be used in the area of maximum brightness (higher illuminance levels or photoconductors with a great photosensitivity). The maximum value of the electrostatic contrast corresponding to the exposure time is written in the following form:

AV _1n -V ₀ / (A), (5) *

c "■ ds + e _s -dp

From expression (6) it follows that a ratio A = IO to 15 is sufficient to achieve high contrasts, because / '(10 to 15) is approximately 1. A further increase in the ratio A above 10 to 15 does not have any noteworthy effect Contrast enhancement.

The above case assumes the formation of an electrostatic latent image only when exposed to light. The necessary exposure time / "can be reduced to t ,," by / V times compared to the charging time / ,, for which the required contrast ,,, has to be generated, if the photoconductive layer consists of a photoconductor with a persistent conductivity is trained. The shortening of the exposure time is due to the fact that an increase in the electrostatic contrast in such a system persists for a certain time after the end of the exposure due to the persistent conductivity.

If the factor for the persistent conductivity A 'after the end of the exposure as a result of a practically instantaneous (short-term) and a slow (long-term) decrease (λΒ < 1) in the time according to the hyperbola law

changes, where γ < 1 and λ, ß, y denote parameters which characterize the temporal decrease in the persistent conductivity of the photoconductive layer after the end of the exposure, the exposure time can be increased by about

/ - / -JL (8)

^s 'ate

decrease while maintaining sufficiently high values of ^ '.

From expression (8) it follows that the exposure time can be reduced by N times, where:

(9) aasstJ

The sensitivity of the thermoplastic material to deformation is fourth Proportional to the power of an electric field applied to the thermoplastic layer. That's why it is expedient to use 0.1 to 3 μm thick thermoplastic storage layers. That makes it possible, proportionally easy to achieve high electric field strengths (with low potential values of the charging device) and to obtain high resolutions, since the degree of deformation with decreasing thickness of the thermoplastic Layer decreases The decrease in the thickness of the photoconductive layer leads to an improvement in the resolution of the recording material because the blurring of a projected optical image with a short drift length of minority charge carriers in the depth of a photoconductor decreases.

The small thicknesses of the layers used facilitate the task of recording materials on a to provide flexible support in the form of a roll.

In the case of the recording material according to the invention, it is not possible to use an electrostatic contrast to be maintained over a longer period of time. This is why it is a step-by-step recording in which the steps the charging, exposure and development run separately in time, impossible. According to the invention hence the steps of charging and exposure at the same time using an on / .eichnungslempcratur preheated thermoplastic storage layer carried out. The invention is concretely photothermoplastic recording material is heated to a temperature between its freezing and their flow temperature. The simplest way is to arrange the recording material on one flat furnace heated to the required temperature with dimensions exceeding the dimensions of the picture, in order to obtain a uniform heating of the edges of the recording material. after the thermoplastic storage layer has been heated to the specified temperature, the charging device becomes switched on and at the same time the image is exposed. Imagewise exposure can also be constant because a non-charged recording material which has no surface potential on the thermoplastic storage layer does not respond to an exposure.

The charge redistribution that occurs under the action of light and an electric field leads to Formation of the electrostatic contrast investigated above. In bright places, those for the thermoplastic Storage layer reaches critical electric field strengths faster as a result of a fluctuating distribution an electrical charge and possible local inhomogeneities in the thickness of the thermoplastic Storage layer, depressions are formed in the thermoplastic layer As the deepening increases, the capacitance of such a section increases and the potential decreases. resulting in a transfer of surface charges in areas with a minimum thickness of thermoplastic Layer causes. In this way there is a self-accelerating process: the process of deepening Leaking charges reinforce this recess in the heated thermoplastic layer. This training the depressions ends when the charge is given the opportunity to use the remaining part of the thermoplastic Layer to penetrate. The high, almost critical electric field strengths therefore cause a reduction the surface charge of the thermoplastic layer due to chaotically arising current microchannels, along which depressions are formed in the thermoplastic layer. At a high The degree of homogeneity of the thickness of the thermoplastic layer is exhibited by that formed along the flow channel Wells have a uniform circular shape with approximately the same diameter (see the figure). the Dimensions of these depressions depend on the viscosity of the material of the thermoplastic storage layer away. In the case of a less viscous material, the thermoplastic material is shifted easier, by which a certain amount of the material is displaced from the center of the channel and towards the Edges are pushed out, so that a kind of "parapet" is formed. The diameter of the local Deformations of the thermoplastic storage layer therefore increase with increasing temperature. The diameter the deformation also increases with the increase in the speed of reaching a critical one electric field strength on the thermoplastic storage layer.

The self-accelerating process of the formation of a depression along a channel leads to a rapid formation of a deformation and makes it possible to register an electrostatic contrast that arises on a recording material with a photoconductive layer, the resistance of which is below 10 ^t2 ohm-cm, which increases significantly increases the number of materials suitable for creating photothermoplastic recording materials and enables their sensitivity to be shifted into the boring region of the spectrum.

Such a recording method eliminates the occurrence of an edge effect. Sections of the photothermoplastic Recording material with a homogeneous charge distribution are with an equal deformed mean statistical density. The increase in the surface charge of the thermoplastic storage layer leads to an increase in the mean statistical density of the number of current channels. This the latter circumstance makes it possible to reproduce halftone images in the form of a different deformation density - a case analogous to the number of blackening points of the silver halide folography - and eliminates the need for halftoning when recording half-tone images.

Another advantage of the recording method according to the invention compared to a cis-flowered formation Roughness images lie in the possibility of a large signal-to-noise ratio by reducing them of the noise on the unexposed portions of the photothermal recording material. this is achieved by the fact that for low recording levels (slightly exceeding the freezing level)

pcratures for thermoplastic materials large values of the shear modulus are characteristic. Consequently there is a limit to the charge beyond which a deformation of the thermoplastic storage layer becomes possible. The charger is switched off at the moment when the forces of the electrostatic Field in the thermoplastic storage layer exceeded this limit at the exposed areas while this limit has not yet been reached in the unexposed sections, deformation occurs of the photothermoplastic recording material only in exposed areas. The signal-to-noise ratio in this case reaches a maximum value.

The solution to the main objects of the present invention - increase in photosensitivity, acceleration of the recording process and achieving large resolutions - becomes thinner by using achieved photoconductive layers and thermoplastic layers of the recording material. Because the thin Layers are more elastic, there was the very advantageous effect that a recording material with a Layer made of an inorganic photoconductor on a flexible substrate could graze.

The execution of the recording material with a flexible layer support is for applications in The field of photo and cinema technology is useful for recording electrical signals by means of a scanning beam. In this case, the main requirement placed on the substrate is its temperature resistance, which makes it possible for it enables thermal loads when applying metal and photoconductor layers through thermal Vapor deposition and information recording and erasure without enduring deformation (distortion). The present invention makes it possible to use film supports for thermoplastic recording materials To use polyethylene terephthalate base known per se.

It was found to increase the elasticity and temperature resistance of the flexible layer carrier as very particularly advantageous, this layer support made of polyethylene terephthalate with a content of 0.05 to 0.5 part by weight of 1,1-diacetylferrocene to be produced. The presence of the 1,1-diacetylferrocene increases the softening temperature of the support to 90 to 100 ° C. The thickness of the support is usually in a Selected order of magnitude from 40 to 200 μπι.

The support material is formed in a manufacturing process that does not use a catalyst will. The polymer film is formed by extruding the melt through a slot nozzle Creation of a layer of uniform thickness on a solid flat surface and through its subsequent Cooling down.

It was found possible to use such a support under practically the same conditions as in a conventional photographic film. In addition to being easy to use, it enables the flexible support based on polyethylene terephthalate with a diacetylferrocene content in the above Ratio to improve the thermal mechanical properties of the recording material as a whole.

When producing the recording material with a support of the specified composition the temperature resistance increases and the warpage decreases due to a decrease in the Longitudinal and transverse shrinkage to 1 to 2%.

The increase in the softening temperature of the substrate makes it possible to increase the working temperature when recording the optical information and thus to regulate the characteristics of a recording material, such as the ratio k and the specific dark resistance. When the support according to the invention is used, the image contrast of the recording material also increases when information is read in reflected light because it is colored brown. The transparency of the recording material described is 35 to 45% at a wavelength of 400 to 1100 nm.

An electrically conductive layer is applied directly to the flexible layer support, which is suitable for a ohmic or blocking resistance to the photoconductive layer ensures. Which have a high injectability for Electroconductive layer having majority charge carriers reduces the photosensitivity of the recording material as a result of high dark currents. In the method according to the invention, from the application of Electrically conductive layers made of various metals such as Ni, Cr, Al, Bi, Sb use.

The demand on the surface conductivity of the electrically conductive layer increases with the decrease in the specific resistance of the photoconductors used in the recording material and with the Enlargement of the area of the exposed image.

The photoconductive layer is now applied to the substrate with the electrically conductive layer.

According to the present invention, the main requirement of this photoconductive layer is that it has a lower resistivity value (10 ¹⁰ to 10 12 ohm · cm) at the recording ^{temperature as compared with previously used optical image recording methods (electrophotography and thermoplastic recording).} This makes it possible to significantly expand the range of materials suitable for the production of recording materials. All photoconductors commonly used in electrophotography (for example selenium, selenium-tellurium, selenium-arsenic mixtures, inorganic semiconductors in binders) can be used when carrying out the method according to the invention if they are bonded with temperature-resistant thermoplastic materials. Carrying out the recording at high temperatures allows the present method to be carried out when the resistance of the photoconductive layer drops to the required values at these higher temperatures.

The strong electrical fields leading to field effects in a photolecular material also serve to implement the method according to the invention, the recording being carried out at limit values for the electrical field strength which reduce the resistance of the photoconductive layer to a required value b ^r > .

For most photoconductors, the temperature increases and / or the electrical power increases Field strength a reduction in photosensitivity - a temperature- and / or field-dependent suppression

reduction of the photoconductivity - to be recorded. In order to ensure high values of sensitivity expediently photoconductor compounds having resistivities of ¹⁰ to 10 ¹² Ohm - cm at not used for recording high temperatures.

Such materials include, above all, the entire group of photoconductors that are used for Vidikon Spcichcr- ■ j plates, for example Sb ₂ S i, Sb ₂ Sc \, As ^ S ι, As ₂ Sc ι and the like.

To increase the temperature resistance of a recording material having selenium as a photoconductive layer, this is preferably used in its monoclinic modification. The exposure space (dynamics of image recording) is determined in the recording method according to the invention by those illuminance levels at which the ratio of dark resistance to resistance of the photoconductive layer reaches values of 10 to 15 in the range of maximum brightness. This is why the best results are obtained when recording weakly illuminated objects on recording materials with photo-slidable layers made up of the most sensitive layers (arsenic triselenide). By changing the manufacturing process for the As ₂ Se3 layers, a wide range of ratios of specific resistances to sensitivities can be obtained for creating recording materials for different purposes by varying combinations of these layers with thermoplastic materials. To create recording materials for the recording process according to the invention, it is advantageous to use solutions of (As ₂ Ss) II- (As ₂ SeS) ₁ compounds which, depending on the value χ, allow the sensitivity limit in the long-wave range and the location of the maximum sensitivity in the visible spectrum.

It is advantageous to add doping additives for arsenic chalcogenides to expand the spectral sensitivity wedge to use. An addition of thallium in an amount of 1 to 7% by weight leads to arsenic riselenide and / or to arsenic trisulfide to a decrease in resistivity and a shift in the spectral Sensitivity range.

To expand the range of spectral sensitivity, the photoconductive layer is made of a amorphous arsenic chalcogenide is formed which is doped with bismuth in an amount of 3 to 10 wt .-%

To increase the photosensitivity, the photoconductive layer made of selenium is of the monoclinic modification manufactured.

Lower resistance materials GaA and Ga ₂ SeJ can also be used.

Since it is in the amorphous modification resistivities of 10 ¹⁰ to 10 "ohm - have cm, they allow the electrostatic image with a maximum contrast on the thermoplastic memory layer within times of 10 ^-2 to 10 ^-3 form s.

With the simultaneous deformation and formation of an electrostatic contrast, according to the recording method according to the invention, such a mode of operation of the recording material is obtained in which the fluctuating increases in the electric field strength in the thermoplastic storage layer lead to local deformations along the current channels. The presence of such current microchannels self-rasterizes the projected image and eliminates blurring of the electrostatic image. As a result, it becomes possible to use a photoconductor heterostructure as the photoconductive layer, which can even be produced from known low-resistance materials with a specific resistance below 10 ⁸ OtIm - cm if the effective total resistance caused by a barrier layer has a value of 10 ° Up to 10 ¹² ohm cm, converted to the total thickness of the heterostructure, guaranteed.This type of design of the photoconductive layer extends the range of its spectral sensitivity since both materials used in the heterostructure contribute to the photo signal obtained, and the photosensitivity increases as a result of more complete utilization the energy of an incident integral radiation. Furthermore, the behavior of the recording material over time is improved in the case of a recording with high illuminance levels.

To shorten the exposure time, the photoconductive layer is preferably produced from a photoconductor with a persistent conductivity (memory effect). The exposure time is shortened by the duration of the persistent conductivity, since the electrostatic contrast under the action of the charging current is a value necessary for deformation achieved. A storage layer that is thermoplastic is applied to the photoconductive layer in such a way that the two layers are in electrical contact with one another. The thermoplastic storage layer is made of a material that is deformed in a temperature range between its freezing and flow temperature by an electric field with a strength of more than 10 ⁶ V / cm.

In the temperature range mentioned, funnel-shaped depressions are essentially formed only those areas of the thermoplastic layer that were exposed are deformed. The deformation unirradiated surface sections is considerably reduced, which means that the sensitivity of the recording material is reduced and the contrast of the recorded image can be improved.

Depending on a desired specific application of the method according to the invention, the thermoplastic storage layer at room temperature (for example when recording on a self continuously moving tape of the recording material) show a noticeable cold flow, or they can be recorded during the formation of the deformations for the purpose of permanent registration Information to be networked. The thermoplastic storage layer can have any coloration. For each specific embodiment of the recording material, however, either the layer or the Supports designed so that they are permeable to a spectral range that corresponds to the sensitivity of the Photoconductor

The recording material is formed so that the thickness of the thermoplastic memory layer becomes smaller is than the thickness of the photoconductive layer, the total thickness of both layers being below 5 μm. Through this when optical information is recorded in the unlit surface areas of the recording

/ calibration material electric field strengths achieved that the resulting electrostatic forces per unit area are 5 to 10% smaller than the value of the shear modulus of the material of the thermoplastic Storage layer at the recording temperature. Thus it occurs in the unexposed areas of the Recording material does not deform, and the recorded image is characterized by a high Contrast off.

In the inventive method, a recording material is used with a storage layer made of a thermoplastic material, whose resistivity is between the freezing and flow temperature (ie, at the recording temperature) is below 10 ^'J Ohm - is cm, wherein the memory layer has a thickness of 0.1 to 3 μm. This makes it possible to increase the resolution of the recording materials, which have both a thermoplastic storage layer made of known materials such as butyl methacrylate: acrylonitrile copolymers, styrene-butadiene-butyl methacrylate copolymers or copolymers of unsaturated

Esters of resin acids, as well as from the terpolymers proposed in the context of the present application the specified compositions can have.

When such layers are electrostatically charged, strong electric fields with a strength of more than 10 ⁶ V / cm are formed and the conductivity of the thermoplastic layer increases. This makes it possible to use copolymers for the production of a recording material which have polar groups which are easily polarizable in an electric field. This made it possible to impart certain predetermined properties to the recording materials while maintaining the desired resolution by changing the composition of the thermoplastic layer.

According to the present invention, for the first time in an advantageous manner for the formation of the thermoplastic Storage layer terpolymers used have monomer units of styrene, alkyl methacrylate and of styrene derivatives with a chemically active residue. You can through the following general formula to be discribed:

CH,

-CH ₂ -CH-CH ₂ -C-CH ₂ -CH-

R COORi / \

35 in the

R is a phenyl, naphthyl, chlorophenyl or fluorophenyl radical,

Ri is a butyl or octyl radical,

X is a hydrogen atom, an alkyl, alkoxy radical or a halogen atom, and

Y is an amino, an isocyanato or isothiocyanato group.

The material of the thermoplastic layer becomes more appropriate through a radical copolymerization Monomers obtained in the presence of an activator. The ratio of the monomers is in the starting mixture chosen so that transparent film-forming thermoplastic materials with the following optimal parameters will be obtained:

Intrinsic viscosity 0.14 to 0.21

Freezing temperature 32 to 6O ^{0 C}

Flow temperature 70 to 86 "C.

The thermoplastic storage layer is made by pouring a solution of a copolymer in a organic solvent, for example in toluene, applied to the photoconductive layer. The thickness of the The thermoplastic storage layer is approximately 1 to 3 μm.

The styrene derivatives with chemically active residues are in particular vinylphenyl isocyanate, vinylphenylamine, Vinylphenyl isothiocyanate into consideration.

A recording material that consists of a thermoplastic storage layer based on a terpolymer Styrene-butyl methacrylate-vinylphenyl isocyanate with a ratio of the monomer components (in mol%) of

Styrene 34 to 38 ω

Butyl methacrylate 56 to 60

Vinylphynyl isocyanate 2 to 6

has, fixes a recorded image up to the flow temperature of the thermoplastic layer, which is achieved by the Introduction of NCO groups into the copolymer is achieved, since this crosslinking of the macromolecules b5 cause during the recording and in the further storage of the recorded information. At the same time, the adhesion of the thermoplastic storage layer to the photoconductive layer increases, which it enables the recording material to be used to produce a large number of copies.

The use of a recording material of the specified ArI eliminates additional operations when copying, such as the production of nickel matrices or an irradiation of the thermoplastic layer with ultraviolet rays to fix the image due to crosslinking of the polymer.

The extension of the memory line for the recorded information without deteriorating the contrast is also achieved when using a recording material * in which the thermoplastic storage shaft on the basis of a terpolymer of styrene-butyl methacrylate-vinylphenylamine with the following ratio of Components (mol- ° / o) is made:

Styrene 30 to 40

ίο Butyl methacrylate 55 to 60

Vinylphenylamine 5 to 10

The images formed on the recording material are stored for an unlimited period of time. The stability of the recorded images allows the recording material according to the invention for the To use multiple copying as photo cliché.

A recording material in which the thermoplastic storage layer is based on a terpolymer from styrene-butyl methacrylate-vinylphynyl isothiocyanate with the following ratio of monomer components (Mol-o / o):

Styrene 30 to 40

Butyl methacrylate 50 to 60

Vinyl phenyl isothiocyanate 5 to 10

is trained. allows. the photosensitive wedge of the recording material compared to the sensitivity of a recording material with a thermoplastic storage layer made of a styrene-butyl methacrylate copolymer to increase, as well as to store the recorded information over a longer period of time.

Virtually complete elimination of cold flow is achieved with the introduction of NCS groups in causes the copolymer, since these cause crosslinking of the copolymer. Which lead to an increase in Overall photosensitivity of the recording material leading to a lowering of the flow temperature of the thermoplastic The storage layer is created by increasing the content of butyl methacrylate members in the copolymer achieved The lowering of the flow temperature of the thermoplastic storage layer also allows to increase the speed of developing and fixing the recorded information.

To increase the photosensitivity while maintaining the other advantageous properties of the Recording material (image fixation, high wear resistance when copying multiple times, increased adhesion inter alia) in the case of a terpolymer of the above type, a halo-glycol is used instead of styrene, the Components are present in the following proportions (mol%):

Alkyl methacrylate 30 to 50

Styrene derivative with a chemically active residue 5 to 15

Halostyrene 35 to 65

When it is necessary to increase the exposure latitude, a terpolymer is preferably used used, which has vinylnaphthalene members at the following ratio of components (mol%):

Alkyl methacrylate 50 to 55

Styrene derivative with a chemically active residue 5 to 10

Vinyl naphthalene 40 to 45

This effect is the result of an increase in the chain of conjugated double bonds when benzene residues are exchanged for naphthalene residues.
The invention is explained in more detail below on the basis of specific exemplary embodiments.

B e i s ρ i e 1 1

A photothermoplastic recording material is used, which has a flexible layer support m'r a polyethylene terephthalate base with a thin chrome coating, a photoconductive layer of arsenic trisene lenid AsaSej with a thickness of 3 μm and a thermoplastic storage layer made of a butyl methacrylate acrylonitrile copolymer with a thickness of 1, 8 μπι includes. The Einfriertemperalur the thermoplastic memory layer is 45.0 ⁰ C, the flow temperature 92 ° C. The recording temperature is set to 65 ° C. The resistivity of the photoconductive layer at this recording temperature is 3-10 "ohm-cm, and that of the thermoplastic layer is 7-10 ¹² ohm-cm. The recording material is placed in a recording device and heated to a recording temperature of 65 ° C. Depending Depending on the illuminance of the object, the aperture of the lens is adjusted in such a way that there

Ratio of the change in the resistance of the photoconductive layer on sections of maximum illumination strength against the dark resistance exceeds a value of 10, d. H. the illuminance amount for the present photoconductive layer 17 1 χ. The geometry of the corona discharge device as well as there Potential at the spray thread are preselected in such a way that during the time of exposure and the simultaneous!

Charging, the electric field strength on the unexposed sections of the recording material is 5 to 10% lower than a value that ensures an ^{electrostatic force per unit area of 0.8 kg / cm 2 corresponding to the amount of the shear modulus of the thermoplastic layer at a temperature of 65 ° C} .

After the aperture has been set in this way, namely to 4, which ensures a resistance change of 10 in the brightest illuminated sections, and the potential of the spray electrode has been set to 6 kV, an image projected onto the aforementioned carrier is produced within a period of t _s = 0.2 s recorded. In this case, the switch-on time of the charging device plays the role of a shutter.

An image is obtained which is formed by fine micro-deformations (approx. 3 μΐη), the distribution density of which increases ^{with the illuminance from 10 to ΙΟ 4 mrn ~ -.} The exposure latitude of the recorded illuminance levels was 2 to 17 1 ×.

Example 2

The same recording material is used as in Example 1 and the recording temperature is set to 80 "C. The specific resistance of the photoconductive layer at this temperature is 1.4-10 'ohm · cm. The shear modulus is reduced to a value of 0. 11 kg / cm ^2. The photosensitivity of the photoconductive layer also decreases, and the ratio for the change in resistance of 10 is reached at an illuminance of 25 1 χ The aperture is increased to a value of 3.5, the voltage at the spray electrode reduced to 4.5 kV, and the charge and exposure time is 0.01 s.

As a result, an image is obtained that μπι of individual micro-deformations with dimensions of about 5 is formed with good reproduction of halftones without edge effect. The exposure latitude is 1 to 25 Ix.

B e i s ρ i e I 3

A recording material is used which comprises a flexible support based on polyethylene terephthalate with a thin chrome coating, a photoconductive layer made of arsenic trisulfide and a thermoplastic storage layer made of a butyl methacrylate-styrene copolymer with a thickness of 1 μm. The freezing temperature is 45 ° C., the flow temperature 29 ° C. The specific effective resistance is 1.2 · 10 ¹² ohm · cm at a thickness of 1.5 μm. The recording temperature is set to 84 ° C. The shear modulus at this temperature is 0.105 kg / cm · ² . The specific resistance of the photoconductive layer at the recording temperature is 1.4 · 10 ″ ohm · cm kV. An image is obtained which is formed by deformations with dimensions of about 3 μίτι, which depicts halftones in an exposure range of 27 to 200 1 χ.

Example 4

A recording material analogous to Example 3 is used, in which the photoconductive layer is made of arsenic triselenide. The recording temperature is set to 70 ° C. At this temperature, the shear modulus is 0.6 kg / cm ² , the specific resistance of the thermoplastic layer is 7-10 ¹¹ OhIT) · cm at a thickness of 0.3 μm and the corresponding resistance is Photoconductive layer 3 · 10 ^lfl ohm · cm At an illuminance of 1 1 χ the ratio of the change in resistance is 8. For an exposure time of 0.1 s and a potential of 6 kV, an image is obtained with an image of halftone gradations in one area of illuminance levels from 0.13 1 χ to 1 1 χ.

Example 5

A recording material is used which has a 50 μm thick flexible layer support on the base of polyethylene terephthalate with a content of 0.5 part by weight of 1,1-diacetylferrocene. On the A photoconductive layer of amorphous ar.senselenide with a Thickness of 2 μπι applied. A toluene solution is poured onto the photoconductive layer applied thermoplastic layer, which is a Tcrpolymeres based on slyrole-butyl methacrylate-vinylphenyl isocyanate and has a thickness of 1.5 μίτι. The monomer components of the terpolymer are as follows Ratio before (mol- ° / o):

Styrene 38

Butyl methacrylate 60

Vinylphenyl isocyanate 2 t> o

Such a thermoplastic storage layer has a freezing temperature of 33 ° C and a flow temperature of 58 ° C. The recording temperature is set to 48 ° C. The specific resistance of the photoconductive layer at this temperature is 10 ¹² ohm · cm. The ratio of the change in resistance during exposure is 10 at an illuminance of 16 1 χ. The charging voltage is given as 4.5 kV. The result is an image formed by local deformations with dimensions of approx. 2 μm, which depicts halftones in an illuminance range from 6 to 20 1 χ. During the recording, there is a crosslinking of molecules, which allows the image obtained to be viewed over long periods of time at increased levels

Temperatures. An image erasure was when a pattern was saved as the flow temperature in the course of 5 Sld. not recorded.

Example 6

A recording material with the same .Schichtfoigc as in Example 5 is used, in which the thermoplastic storage layer has a thickness of 3.2 μm and consists of a terpolymer styrene-butyl methacrylate-vinylphenylisothiocyanal consists of the following component ratio (mol%):

to styrene 30

Butyl methacrylate 60

Vinyl phenyl isothiocyanate 10

The freezing temperature is 55.degree. C., the flow temperature is 70.degree. C. The recording temperature is set to 60.degree

Ij set. At this temperature the specific resistance of the photoconductive layer is 10 "Ohm - cm, and at an illuminance of 28 1 χ the ratio of the change in resistance is 9.

The result is an image formed by local deformations with dimensions of approx. 2.5 μΐη, which is halftones in an illuminance range from 2 to 25 1 χ.

Example 7

A recording material with the same layer sequence as in Example 5 is used, in which the thermoplastic storage layer is 2 μm thick and consists of a terpolymer styrene-butyl methacrylate-vinylphenylamine with the following component ratio (mol%): 25

Styrene 32

Butyl methacrylate 60

Vinylphenylamine 8

The freezing temperature is 45 ° C, the flow temperature 82 "C. The recording temperature becomes 68 ° C selected The specific resistance of the photoconductive layer is at this temperature 2.5-10 "ohm · cm, and the ratio for change in resistance of 10 becomes at illuminance of 35 1 χ achieved. An image formed by local deformations with dimensions of 1 μm is obtained, that reproduces semitones in a range of 10 to 40 1 χ. The images obtained can be of any length get saved. The durability of the recorded images enables the recording material to be used for multiple copying.

Example 8

A recording material with the same layer sequence as in Example 5 is used, in which the thermoplastic storage layer has a thickness of 3.5 μm and consists of a terpolymer of octyl methacrylate-vinylnaphtha-un-vinylphenyl isothiocyanate with the following component ratio (mol%):

Octyl methacrylate 50

Vinyl naphthalene 40

Vinyl phenyl isothiocyanate 10

The glass transition temperature is 54 ° C and the flow temperature of 67 Ohm "C, the recording temperature is set at 60 ⁰ C. The specific effective resistance of the photoconductive layer is 5.8 × 10 at the recording temperature." - cm, and a ratio of 9 for the resistance change is achieved at an illuminance of 28 1 χ The potential of the spray thread is 5 kV, the charging and exposure time 0.4 s. An image formed by tocal deformations with dimensions of about 2 μm is obtained. The exposure latitude for the illuminance levels recorded by the recording material is 0.2 to 26 1 χ.

Example 9

A recording material with the same layer sequence as in Example 5 is used, in which the thermoplastic storage layer has a thickness of 1.5 μm and consists of a terpolymer of octyl methacrylate-fluorostyrene-vinylphenylamine with the following component ratio (mol%):

Octyl methacrylate 50

Fluorostyrene 35

Vinylphenylamine 15

The freezing temperature is 35 ° C, the flow temperature 64 ° C. The recording temperature is adjusted to 50 ⁰ C. At this temperature, the specific contact resistance of the photoconductive layer is 9 - 10 ^u ohm-cm, and a ratio of 10 for the resistance change is χ achieved at an illuminance of 16. 1 The image formed on the recording material is affected by local deformations

Dimensions of 2.5 μιη formed and gives Halblönc in an illuminance range of 0.2 to 26 1 χ again.

Example 10

A recording material is used with a flexible layer support which has a polyethylene terephthalate base with a conductive chromium coating layer and which has, as the photoconductive layer, an arsenic triselenide layer with a thallium doping in an amount of 5% by weight which is vapor-deposited in vacuo . The thickness of the photoconductive layer is 2 μιη, the specific dark resistance at the recording temperature 5 -10 "ohm · cm. With a striking energy of 5 · 10 ~ ⁷ J / cm ² and a wavelength of the light used of 0.7 μίτι the ratio the change in resistance of the photoconductive layer is equal to 15. A thermoplastic storage layer made of a terpolymer of the following composition is applied by casting:

30 mol% styrene, 60 mol% butyl methacrylate and
10 mole percent vinyl phenyl isothiocyanate.

The thickness of the thermoplastic storage layer is 1.5 μm, the freezing temperature 55 ° C, the flow temperature 70 ° C. The elastic modulus at the recording temperature is 0.12 kg / cm ² .

The image recording is carried out under preheating the Aufzeichnungsmateriais to a temperature of 6O ⁰ C and at a voltage to the discharge electrode of 4.5 kV. The charging time is equal to the exposure time and is 0.2 s. It is exposed to light of different wavelengths in a range of the incident energy of 3 × 10 ^-8 to 10 ^-6 J / cm ^2. An image formed by local deformations of the thermoplastic layer with dimensions of 1 μm is obtained for wavelength ranges from 0.5 to 1 μm. The spectral sensitivity of the recording material used is thus shifted by 0.2 μm into the long-wave range compared with a recording material using undoped arsenic triselenide.

Example 11

A recording material with the layer sequence described in Example 10 is used in which the 2 μm thick photoconductive layer is composed of arsenic selenide doped with bismuth in an amount of 7% by weight. The specific dark resistance of the photoconductive layer at the recording temperature is 7 ^{× 10 10} ohm · cm.

For image recording, the recording material is heated to a temperature of 6O ⁰ C and the voltage on the discharge electrode is set to 4.5 kV. The charging time is equal to the exposure time and is 0.05 s. The exposure takes place with radiation of different spectral composition in a wavelength range from 0.6 to 1.0 μm with energies from 10- "* to 10 ~ ⁷ J / cm ² .

A deformation image in the wavelength range from 0.6 to 1.0 μm is formed on the recording material the end. The range of spectral sensitivity exceeds the range of spectral sensitivity of one Recording material using undoped arsenic triselenide by 0.2 μm.

Example 12

A recording material with the same layer sequence as in Example 10 is used, in which the 1.5 μm thick thermoplastic storage layer made of a terpolymer styrene-butyl methacrylate-vinylphenyl isocyanate with the following component ratio (mol%):

Styrene 38

Butyl methacrylate 60

Vinyl phenyl isocyanate 2

The freezing temperature is 33 ° C., the flow temperature 58 "C. The foil-conductive layer has a thickness of 2.5 μm and is made from selenium of the monoclinic modification. Its specific dark resistance is 10 ¹⁰ ohm · cm. The ratio of the change in resistance is at an illuminance of 2 1 χ equals 15.

For image recording, the recording material is heated to 48 ° C. and charged with a Spray electrode with a voltage of 4.5 kV. At the same time the recording material is used for a period of time exposed for 0.1 s. The projected image is in the form of local deformations of the thermoplastic storage layer that reproduce halftones in a range of illuminance levels from 0.1 to 2 1 χ. the low values of the registered illuminance levels show a considerable increase in the sensitivity of the used recording materials for single use compared to recording materials on the Base of other photoconductive layers.

B e i s ρ i e I 13 ö5

A recording material with the same layer sequence as in Example 10 is used, in which the photoconductive layer has a thickness of 2 μm and is made of amorphous gallium triselenide. In the

Recording temperature, the specific dark resistance of the photoconductive layer is 10 ¹⁰ ohm · cm. The ratio for the change in resistance is 1 χ 15 at an illuminance of 12.

The image is recorded with a recording material at a temperature of 60.degree. The voltage of the spray electrode is 4.5 kV, and during charging there is an exposure for a period of 0.01 s carried out An image is formed that contains halftones for an illuminance range of 5 to 12 1 χ with short charging and exposure times.

Example 14

ίο A recording material with the same layer sequence as in Example 10 is used, whose 2.5 μm thick photoconductive layer is made of a cadmium chloride with persistent conductivity. The specific one Dark resistance of the photoconductive layer at the recording temperature is 10 '"ohm · cm. A ratio of 10 for the change in resistance is achieved with an illuminance of b 1 χ. Of the The value of the persistent conductivity is 80% of the previous one 1 second after switching off the exposure Worth.

For image recording, the carrier is preheated to 60 ° C. At the same time, the voltage at the spray electrode (4.5 kV) and the exposure are switched on. The exposure time is 0.01 s. The exposure is then stopped and the carrier is charged for a further 0.5 s continued The development and intensification of the image contrast take place after the exposure is switched off due to the persistent leilability

Example 15

A recording material with the same layer sequence as in Example 10 is used, in which a heterostructure based on cadmium sulfide and arsenic selenide doped with thallium in an amount of 5% by weight is used as the photoconductive layer. The layer thickness of the cadmium sulfide is 1 μm, and a ratio of 10 for the change in resistance during exposure is achieved at an illuminance of 11 χ. The specific dark resistance is 10 ^l "ohm-cm. The layer thickness of the thallium-doped arsenic selenide is 1.5 μm. The specific total effective resistance of the photoconductive layer is 10 ^u ohm-cm. During image recording, the recording material is ^{heated to a temperature of 60 °} C. and charged by a corona discharge at a voltage of 4.5 kV at the spray electrode is equal to the exposure time and is 0.5 s. The image is formed in the form of local deformations of the thermoplastic layer with differences in the deformation density between sections of different illuminance levels.

Example 16

The recording material has a 50 μm thick flexible layer support based on polyethylene terephthalate which contains 0.5 part by weight of 1,1-diacetylferrocene. The layer support is 50 nm thick Electrically conductive chromium layer vacuum-deposited onto this chromium layer, likewise by means of vacuum deposition applied a photoconductive layer of amorphous gallium selenide a thickness of 3 μm. on this layer is a 2 μm thick layer of a terpolymer by pouring on a toluene solution Styrene-butyl methacrylate-vinylphenyl isocyanate are present (MoI-%):

Styrene 38

Butyl methacrylate 60

Vinyl phenyl isocyanate 2

The thermoplastic layer obtained has an intrinsic viscosity of 0.21, a glass transition temperature of 33.degree. C. and a flow temperature of 58.degree. The recording temperature of the recording material was 48 ° C. and the potential of the spray electrode was 4.5 kV. The sensitivity of the recording material was 10 ⁷ cm ² / yr. The storage time for the image is practically unlimited ^{at a temperature of 20 ° C}

Example 17

The recording material has the same layer sequence as in Example 16 and is in the same way manufactured

The thermoplastic layer is 3 μm thick and consists of a terpolymer styrene-butyl methacrylate-vinylphenylamm with the following component ratio (mol%):

Styrene. 32

Butyl methacrylate .60

Vinylphenylamine 8

The intrinsic viscosity of the thermoplastic layer is 0.17. the freezing temperature 45 ° C and the flow temperature 82 ° C. The recording temperature was 65 ° C. the potential of the spray electrode 4.5 kV. The sensitivity of the recording material is 10 ⁷ cm ² / J.

Claims (19)

Patent claims: 1. Photo-thermoplastic recording process for optical information on a recording material with a film-permeable layer and with a thermoplastic memory layer. that the ■ 3 processes of a charging of the thermoplastic storage layer, an imagewise exposure of the photolite capable layer, heating and cooling of the recording material to fix a through Includes surface roughness wedges of the thermoplastic storage layer formed visible image, characterized, to a) that the thermoplastic storage layer of the recording material on one of a temperature range between its freezing and its flow temperature selected temperature is preheated, the is maintained until the end of charging and imagewise exposure, b) that the charging and the imagewise exposure of the recording material take place simultaneously, c) that the charging rate of the thermoplastic layer is such that the electrostatic forces per unit area in the unexposed areas of the recording material are 5-10% smaller as the value of the shear modulus of the material of the thermoplastic storage layer at the recording temperature, d) that the illuminance is so dimensioned. that in the areas of maximum brightness the The resistance of the photoconductive layer to the dark resistance changes by 10-15 times, e) that the time for charge and imagewise exposure by the equation is determined where t _{s is} the charging time, / n, the exposure time, τ is the dark relaxation time for the charge on the recording material and k is the ratio of dark resistance to resistance of the photoconductive layer in the region of maximum brightness, or f) that alternatively, when using a photoconductive layer with memory effect, the exposure time i _m is reduced by N times compared to the charging time t _s , the value N according to the equation α · β - Uj
35 is determined in the <x, ß, γ denote parameters that characterize the temporal decrease in the persistent conductivity of the photoconductive layer after the end of the exposure. 2. Recording material for carrying out the method according to claim 1, with an electrically conductive one Layer base, a photoconductive layer made of an inorganic photoconductor and a thermoplastic Storage layer on the photoconductive layer, characterized in that a) that the thermoplastic storage layer has a resistivity below 10 ^l3 ohm cm within a temperature range between its freezing temperature and its flow temperature and is in electrical contact with the photoconductive layer, b) that the photoconductive layer in the temperature range specified under a) has a specific resistance between 10 ¹⁰ and 10 ^I2 ohm-cm, which, however, is at least a factor of 10 within the specific resistance of the thermoplastic storage layer, wherein c) the total thickness of the photoconductive and the thermoplastic storage layer is below 5 μm 3. Recording material according to claim 2 for performing the method according to claim 1 according to Feature f), characterized in that the photoconductive layer consists of an inorganic photoconductor with persistent conductivity is established 4. Recording material according to claim 2 or 3, characterized in that the photoconductive layer is made from an amorphous arsenic chalcogenide mixed with thallium in an amount of 1-7% by weight is endowed 5. Recording material according to claim 2 or 3, characterized in that the photoconductive layer is made from an amorphous arsenic chalcogenide, which is mixed with bismuth in an amount of 3–10% by weight is endowed 6. Recording material according to claim 2 or 3, characterized in that the photoconductive layer is made from selenium of the monoclinic modification. 7. Recording material according to claim 2 or 3, characterized in that the photoconductive layer is made from amorphous gallium chalcogenide 8. Recording material according to claim 2 ^ or 3, characterized in that the photoconductive layer has a two-layer structure, the materials of the individual layers each having a specific resistance of less than 10 ⁸ ohm cm and the effective total resistance of the photoconductive layer between 10 ¹⁰ and 10 ¹² ohms - cm. 9. Recording material according to one of Claims 2 to 8, in which the thermoplastic storage layer made of a plastic based on copolymers of vinyl aromatic hydrocarbons and Alkyl methacrylate is produced, characterized in that the thermoplastic storage layer is made of a terpolymer of a vinyl aromatic hydrocarbon, an alkyl methacrylate and a Styrene derivative with a chemically active radical which is an isocyanate group, an amino group or a Isothiocyanate group, there is, wherein the styrene derivative with the chemically active radical in one Amount of 2 to 10 mole percent of the terpolymer is present. 10. Recording material according to claim 9, characterized in that the thermoplastic storage layer is made from a terpolymer made from the following monomer components (in mol%): Styrene 34-38 to Butyl methacrylate 56-60 Vinyl phenyl isocyanate 2-6 11. Recording material according to claim 9, characterized in that the thermoplastic storage layer is made from a terpolymer made from the following monomer components (in mol%): Styrene 30-40 Butyl methacrylate 55-60 Viny Iphenylamine 5-10 12. Recording material according to claim 9, characterized in that the thermoplastic storage layer is made from a terpolymer made from the following monomer components (in mol%): Styrene 30-40 Butyl methacrylate 50-60 Vinyl phenyl isothiocyanate 5-10 13. Recording material according to claim 9, characterized in that the thermoplastic storage layer from a terpolymer with the following monomer component composition (in mol%) is made: Alkyl methacrylate 50-55 Styrene derivative with the chemically active residue 5–10 Vinyl naphthalene 40-45 14. Recording material according to claim 13, characterized in that the thermoplastic storage layer is made from a terpolymer made from the following monomer components (in mol%): Octyl methacrylate 50-55 Vinyl phenyl isocyanate 5-7 Vinyl naphthalene 43-47 15. Recording material according to claim 13, characterized in that the thermoplastic storage layer is made from a terpolymer made from the following monomer components (in mol%): Octyl methacrylate 50-55 Vinylphenytamine 5-10 Vinyl naphthalene 40-45 16. Recording material according to claim 13, characterized in that the thermoplastic storage layer is made from a terpolymer made from the following monomer components (in mol%): Octyl methacrylate 50-55 Vinyl phenyl isothiocyanate 5-10 Vinyl naphthalene 40-45 17. Recording material according to one of claims 2 to 8, in which the thermoplastic storage layer is made from a plastic based on copolymers of alkyl methacrylates, thereby characterized in that the thermoplastic storage layer consists of a terpolymer from the alkyl methacrylate, a halostyrene and a styrene derivative with a chemically active residue that is an isocyanate group, an amino group or an isothiocyanate group, is prepared, the monomer component composition (in mol%) is within the following limits: Alkyl methacrylate 30-50 Styrene derivative with a chemically active residue 5-15 t ^r > Halostyrene 35-65 18. Recording material according to claim 17, characterized in that the thermoplastic storage is made of a terpolymer from the following monomer components (in mol%): Octyl methacrylal 30-50 Vinyl phenyl isocyanate 5-7 Halostyrene 35-63 19. Recording material according to claim 17, characterized in that the thermoplastic storage shaft is made from a terpolymer of the following monomer components (in mol%):