Untitled record

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The present invention relates to a multilayer film containing the color developing compounds which individually distinguishable. Furthermore the invention relates to a process whereby imaging of such film is effected in 5 a variety of colors that can be distinguished.

PRIOR ART Monolayered color imaging with leuco base compounds, fixedly positioned in a binder, is known. Generally, the leuco base together with an acid generating activator is dispersed in a binder 10 and the dispersion is coated onto a conductive support. When exposed to radiant energy, such as photon or particle radiation, acid is liberated from the activator and the ensuing reaction between the acid and the leuco base produces an image in a color corresponding to the dye product. Asset-15 engine is usually a low molecular weight compound containing labile halogen from which hydrogen halide is liberated as a result of exposure to radiant energy. Such a process is described in U.S. Patent 3,560,211. Such films are subject to damage or deterioration by exposure 20 from heat and light during normal storage since the activator compounds often cause unwanted predevelopment by formation of acid and concomitant reaction of this product with the leuco dye. When used in a high vacuum environment as in the case of exposure to electron beams has 25 including such films tend to lose the activator reactants owing to their volatility at reduced pressures and do not develop full image intensity. Such films are not adaptable to multilayer imaging since the amount of volatilized activator is not easily controlled and the removal of the activator-product from lower layers would be extremely difficult and most probably would cause damage to any superimposed imaging layer.

Furthermore, the loss of volatile components in the film in the high vacuum environment 55 in an electron beam exposure apparatus harmful to the prolonged error free functioning of said device because 0:02 these volatile components are adsorbed onto and contaminating the surfaces inside the electron optical column.

Alternatively, oil soluble amino azo 5 dyes, which change color at a pH between 2 and 4 have been substituted for the leuco base compounds since such compounds, as described in US patents 3,370,981 and 3,425,867, have relatively low volatilities. These azo compounds require close control of pH at 10 imaging layer to effect proper color development and often produce unstable conditions, which problems would be multiplied in a system employing several superimposed imaging layers.

15 Mono Color imaging with polyacetylene crystals fixedly positioned on a base film is also known as described in U.S. Patent 3,501,302. Because of the large discrepancy between leuco base compound and polyacetylene compound sensitivity responsive to exposure dosages are 20 required for imaging, these materials have been regarded as incompatible in the same system.

It is accordingly an object of the present invention to overcome the above disadvantages and to provide 1:25 commercially acceptable multilayered imaging film for development in several colors distinguishable from each other by an efficient and commercially viable process.

Another object of the invention is to provide 1:30 electron recording film which requires no development, fixing or other processing subsequent to exposure in order to provide a multicolored image.

A further object of the invention is to provide 1:35 multilayered imaging film which is not subjected to degradation from exposure to moisture, light or heat.

3

Another object of the invention is to provide a multilayered imaging film which minimizes volatilization of components during radiant energy exposure at high vacuum and which provides a color stable image.

5

A further object is to effect multicolored imaging with a lower expenditure of radiant energy.

Yet another object is to provide a method for 10 transducing electrical information into a multicolored visual record.

These and other objects of the invention will become apparent from the following description.

15

According to the present invention there is provided a recording medium having a plurality of superimposed color imaging layers, disposed on a conductive support, which are capable of individual color development at discrete points of address when exposed to 20. a source of radiant energy. The film comprises a first or surface imaging layer composed of a normally solid, aliphatic halogenated polymeric binder capable of undergoing dehydrohalogenation in response to energy from a source of radiant energy at a 25 hits point and homogeneously dispersed therein have. one polyphenyl leuco base capable of forming a corresponding ionized halide salt by interaction with the hydrogen halide generated from the halogenated polymer; a separate image-forming layer in which is fixed a photosensitive sensitive polyacety-J0 lenisk compound having at least two acetylenic linkages in a conjugated system; said layer containing the polyacetylenic compound is provided below the first layer, and can form a dye of a color distinguishable from that which will be developed in the first layer and 55 an electrically conductive support for the above-described image-forming layer.

* 4

While the preferred film of the invention comprises two imaging layers, namely a first or surface image-forming layer containing the uniformly dispersed polyphenylmethane leuco base and a second layer containing the uniformly 5 dispersed polyacetylene compound which second layer is contiguously disposed below the first layer , it is understood that films having multiple color distinguishable leuco base layers and / or layers containing color distinguishable poly-acetylene compounds are also covered by the present up-10 inventive. A tri-color image can also be obtained with only two imaging layers. This is accomplished by selecting a thermochromic polyacetylenic compound by heating to a temperature between about 60 and ca. 140 ° C, depending on the compound, converts an image in its original color to 1:15 completely different tint. This color conversion is permanent so that re-exposure of the same polyacetylenic layer with a different image at a lower temperature, for example. less than 50 ° C, evoking the second picture in the original color shade or color. Accordingly, a 20 two-color image obtained in the polyacetylenic layer and a monochrome image in the leuco dye layer. When films containing three or more color developing layers are employed, the leuco base layer or layers are disposed nearer the surface and are applied over the polyacetylene layer or layers so as to 25 prevent, the exposure of the more sensitive color developing polyacetylene. To simplify the description, the following discussion is directed mainly to the imaging films containing only two layers.

j0 process for color development of the above described film depends on the observance of critical parameters, primarily the use of several different and critical beam energies and exposure dosages modulated to effect separate penetration, exposure and imaging of the first J5 imaging layer and first and second imaging layers in combination and to cause generation of hydrogen halide from said halogenated polymer in said first layer, * 5 point of beam impact with simultaneous formation of the halide salt dye and to cause direct color development of the polyacetylenic compound in the second layer, 5 imaging the film requires that the energy be selected which is sufficient to penetrate the individual layer to be induced and the use of concomitant exposure dosage sufficient to effect color development in the specified layer. The order of lagbildedannelse 10 is not critical so pro¬ vided either the first layer or first and second layers can be subjected to the initial stråleenergiekspo-exposure. Because of the large difference between leuco base and polyacetylene sensitivity, are in each case imaging is effected in the true and original color of 15 color developing compound, and color blending, as in the case of multilayered films containing different leuco bases in a dehydrohalogenatable binder, is entirely eliminated. Hence strongly contrasting colors and attractive formats obtained with the present films.

20

The beam energies are controlled in accordance with the thickness of each individual imaging layer, such that when a surface or first imaging layer of the present film is employed in a thickness of between about 0.1 and ca. 8 micrometers, 25 is preferably between about 0.5 and ca. 4 micrometers, a corresponding electron beam energy of from about 1 to ca. 30 KeV, preferably from about 5 to ca. 20 keV, necessary for adequate penetration.

30 An exposure dosage of between about 1 x 10-7 and about 1 x 10 "1 C / cm2, preferably between about 1 x 10- ^ and about 1 x 10 <C / cm2, used to effect the dehydrohalogenation of the leuco base binder and to develop the corresponding halide salt dye. The second underlying imaging layer, 35 which typically has a thickness between about 0.1 and about 10 micrometers, preferably between about 0.5 and about 5 micrometers, requires en'høyere beam energy in the range between about 5 and about . 40 KeV, t 6, preferably between about 10 and about 30 KeV, for adequate penetration through the first and into the second imaging layer. because of the higher the sensitivity of the polyacetylenic compound is however 1:05 significantly lower exposure dose than the used for the first layer is necessary. Generally, an exposure dose of between about 1 x 10-4® and about 1 x 10 "® C / cm2, preferably between about 1 x 10 "^ and about 1 x 10 "®, used for inducing the polyacetylenic dye. The above 10 parameters or equivalent energies and dosages for other sources of radiation must be strictly observed for color stable, multicolor development of the present film.

Due to the higher sensitivity of the polyacetylenic 15 cal film is less residence time for development of an image is necessary, eg. from about 10 "8 to about 10 "® seconds, at an exposed dosage of 10" ^ to 10-7 C / cm2. In contrast, a dwell time of about 10 "5 to about 10.8 seconds required for the leuco base surface layer at a 20 exposure dose of 10 "® 10" 4 C / cm2.

As indicated, each electron beam possesses a small and final gjennomtrengnlngskraft and beam energies and layer thicknesses utilized in the present invention must be carefully 25 controlled within the above ranges. Such control is obtained through the degree of acceleration of electrons in the electric field between the anode and cathode of an electron beam apparatus. Failure to apply the correct electron beam energy can not be corrected by adjusting the degree of 30 film exposure because it is of primary importance that the beam penetrate the layer to be imaged. Thus, no matter how high the beam intensity, no image will be developed when the beam energy is too low to penetrate the imaging layer selected.

35

It is particularly preferred that at least the higher beam energy, required for the underlying July 2 layer, be effected by energy transmitted from an electron beam; beam thousands Glen used for both layers may bevlrkes with the same or different particulate energy source, if desired.

5

Although it is preferable to effect development of the second imaging layer before imaging the surface layer, the order of exposure reversed without departing from the present invention.

10

Radiation Kitchener Glen contemplated as the energy source in the present invention includes energy generated from an electron beam such as developed by cathode ray guns, ion beams, uncharged particle beams such as molecular-15 rays, Ύ-rays and X-rays used in radiography, β-rays, electron -koronautladning, ultraviolet and actinic radiation, radiation from visible and infrared regions of the electro magnetic spectrum and other forms of corpuscular and / or wave-like energy generally deemed to be 20 radiant energy.

The preferred source of exposure employed in the present invention is an electron beam. Generally, the electrons, under high vacuum between about 10 ~ 8 and about 10 <torr, preferably 25 show between about 10 <and about 10-8 torr, at the modulated beam energy required to penetrate and image the selected imaging layer, bombard the selected layer of the film and effect color development into an optical display. In the layer containing the polyacetylenlske connec- 3o DEIS obtained directly color development. In the layer containing the leuco base compounds bombards however electrons the halogenated polymeric binder causing generation of hydrogen halide and simultaneous reaction of the polyphenylmethane dye precursor with the hydrogen halide to give 35 its corresponding halide for color development by electron impact point. the techniques. electron registration is well known and further description is therefore not necessary 8. for illustrative purposes, however, a conventional electron beam recording operation suitable for the present invention may utilize an electron beam characterized by having a beam diameter of about 1 to 5 about 100 micrometers, an amperage of about 10_ <? to 5.10 amp and adapted to scan a target at a rate such that the residence time is from about 8.10 to 3.10 seconds. Vacuum Pressure in film chamber usually ranges from about 10-3 to 10-8 torr.

10 Generally, an exposure can be effected by any radiant source including photons, UV light with a wavelength of less than 3000 Å, røntgentstråler, Ύ-rays, β-rays, one ion beam, a molecular beam of uncharged particles, and electron beam, the electron beam is the energy source 15 preferred.

The normally solid, halogenated polymers selected for the first or leuco base imaging layer in the present invention function as binders for the homogeneous distribution 20 of the polyphenylmethane dye precursor and corresponding dyes throughout the layer. These polymers contain between about 10 and ca. 90 wt-36, preferably between about 40 and ca. 70 wt-56, labile halogen and are selected from the group of aliphatic polymers such as for example. polyvinyl halide, polyvinylidene halide 25 and their copolymers containing a minor amount, preferably less than about 25 ^, of comonomers such as trichlorethylene, dichlorodifluoroethylene, vinyl acetate or lower alkyl acrylate or methacrylate. Halide moiety of the polymers can be chlorine, bromine or iodine, but they J0 chlorine containing polymers are preferred and polyvinyl chloride and polyvinylidene chloride homopolymers or vlnylklorid / vinylidene copolymers are most preferred.

Polyphenylmethane invention represents j5 a restricted class of leuco base compounds which are capable of reacting with hydrogen halide to form an ionized halide salt dye, preferably chlorine salt dye.

f 9

In general, these phenylmethane compounds represented by the formula: B - E - B 'where A, B, A' and B 'are independently hydrogen or lower alkyl and alternatively A taken with B and N or A' taken with B 'and two N form a 4-6 membered heterocyclic ring; D is hydrogen or hydroxy and E is hydrogen, phenyl or naphthyl which

aryl radicals can be usubstitnerte or substituted by A

/ -N, Chlorine, bromine, lower alkyl or mixtures of these 15 \

B

substituents, or D and E together represent an imino group directly bonded to the carbon = NA.

Examples of .To polyfenylraetan dye precursors, 20 preferably diphenylmethane and triphenylmethane precursors, together with their corresponding halide salt dyes are presented in the following table.

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»14

The second or underlying layer of the imaging film comprises polyacetylenic microcrystals solid suspended and evenly distributed in the binder material in a concentration between ca. 10 and ca. 90 weight percent, preferably between about 5 40 and ca. 70 percent by weight with respect to the binder. The liquid dispersion of normally crystalline polyacetylenic compounds may or may not be aged before drying and imaging according to the method described in my copending patent application. 773,487, filed 5 September 10, 1985. In general, the image receptive polyacetylenic compounds of the present invention includes any of the described in U.S. patent 3,501,302. The preferred polyacetylenic compounds are the conjugated diynes, particularly hydrocarbon or acid diynes 15 containing 20 to 30 carbon atoms. A general formula for these preferred acetylenic compounds is represented by the structure A- (CHG) nC = C-CEC (CH2) mB, wherein m and n are each independently an integer of 0 to 14 and A and B are independent methyl or carboxyl groups. Specific examples 20 of such polyacetylenes include pentacosa-10,12-diynoic acid; 13.15-oktakosadiyn and docosene-10,12-diyne-l, 22-dioinsyre. Of these, pentacosa-10,12-diynoic acid is most preferred since it provides unusually high sensitivity to electron beam exposure. It should be understood that the dispersions of 25 other color developing polyacetylenes having a conjugated structure can be used alone or in admixture with the preferred diynes as the second image receptive layer of the present invention. Such compounds include the diynes of the above structure wherein the A and / or B moieties 1:30 addition to lower alkyl or carboxyl, also can be hydroxy, amido, lower alkyl substituted amido, an aliphatic or aromatic carboxylate ester group having up to 10 carbon atoms, an monovalent or divalent karboksylatmetall salt group, halo, carbamyl, lower alkyl substituted carbamyl or tosyl 35 and the corresponding triyne and tetrayne products of the above polyacetylenes having from 20 to 60 carbon atoms and a conjugated structure. Examples of these "15 compounds include 10,12-docosadiynediol, the ditoluene-p-sulfonate of 9,11-eikosadiynoinsyre, monoethyl ester of 10.12- docosadiynedioic acid, sodium or potassium salt of 10.12- pentacosadiynoic, 10,12 docosadiyne, 10,12- 5 pentacosadiyne (m-tolyluretan), 10,12-pentacosadiyne {[(butoxycarbonyl) methyl] urethane), N- (dimethyl) -10.12-pentakosadiynamid, N, N'-bis (alpha-methylbenzyl) -10.12-pentacosadiyndiamide, triakonta- 16,18,20-triynoinsyre, etc.

10 In the preparation of these films they may polyacetylenic crystals f ø rstdi latches arrange say a non-oppløsellggjørende liquid binder of plastic, resin, colloid or gel and coated on a suitable conductive substrate to a thickness of "ca. 0.1 to ca. 10 micrometers. The polyacetylene binder is selected for its insolubility 15 in the non-aqueous solvent used to prepare the surface-imaging layer of leuco base polyphenylmethane thereby maintaining the integrity of the polyacetylenic layer during coating with the surface layer. Polyacetylene binders which are soluble 20 in the aliphatic polymeric binder of the polyphenyl cause softening and distortion of the substrate and / or mixing with the top layer to the detriment of image quality. Upon drying the dispersion, crystals become fixedly positioned in the binder. The drying operation is conducted over a period of about

25 20 seconds to about 10 hours at from about ambient temperature up to about 100 ° C, and is effected preferably at from 15 ° C to 60 ° C for a period of from about 1 minute approx 5 hours.

Examples of binder materials include natural and J0 synthetic plastics, resins, waxes, colloids, gels and the like including gelatins, desirably photographic-grade gelatin, various polysaccharides including dextran, dextrin, hydrophilic cellulose ethers and esters, acetylated starches, natural and synthetic waxes including paraffin, 55 beeswax, polyvinyl-polymers of acrylic and methacrylic esters and amides, hydrolyzed interpolymers of vinyl acetate and unsaturated addition polymerizable addition compounds such as 9:16 malelnsyreanhydrld, acrylic and methacrylic acid esters and styrene, vinyl acetate polymers and copolymers and their derivatives including fully and partially hydrolyzed products thereof, polyvinyl acetate, polyvinyl alcohol, polyethylene oxide, 5 polyvinylpyrrolidone, polyvinyl acetals including polyvinyl acetaldehydeacetal, polyvinyl chloride, polyvinyl sodium o-sulfobenzaldehyde acetal, polyvinyl formaldehyde, and several other known photographic binder materials including a substantial number of aforelisted useful 10 plastic and resinous substrate materials which could be provided in the form of a dopant solution, dispersion, gel, or the like for incorporation therein of the photosensitive polyA cetyleniske composition and then capable of processing to a solid form containing dispersed crystals of the photosensitive-15 sensitive, crystalline polyacetylenic fabric composition.

As is well known in the art regarding the preparation of smooth uniform continuous coatings of binder materials may be employed therewith small amounts of conventional coating aids as viscosity controlling agents, surfactants 2o agents, leveling agents, dispersants, and the like.

The particular binder material employed is selected with due regard to the specific radiant energy and technique to be employed in the particular image-recording application and invariably is a binder material permitting 25 substantially transfer or penetration of that specific radiant energy to be used.

Because the crystal size of commercially available, normally crystalline polyacetylenes is relatively large and of 3o varying dimension and since for the coatings of inventive formation microcrystalline size between about 0.01 and ca. 5 micrometers, preferably between about 0.05 and ca. 0.2 micrometers, is most desirable, it is generally recommended that the commercial polyacetylenes first dissolved in a solvent from which 35 later can be recrystallized as fine discrete crystals of a more uniform size, as indicated in said patent application serial no. 773,487, filed 9 . september 1985.

17

Alternatively, the polyacetylenic compound in the present invention is placed as a surface layer of 2-dimensional ordered phase on the substrate. Polyacetylenes containing 5 least one hydrophobic group and at least one hydrophilic group are particularly adapted for the production of parent 2-dimensional phases and include the conjugated diynes, triynes and tetraynes in polyacetylene 10-60 carbon atoms. Preferred of these are Polyacetylenes diynes of the above 10 formula having 20 to 40 carbon atoms wherein either A or B is a hydrophobic group such as linear or cyclic alkyl radicals having 1-12 carbon atoms or aryl of 6-9 carbon atoms and the rest of the substituent A or B is a hydrophilic group such as a sulfonic acid, phosphonate, 15 sulfonate, carboxylate, primary amino, primary amido, carboxyl or hydroxy group. Examples of these include l-phenyl-10,12-docosadiyne-22-ol, (4-methyl) -16,18- triacontadiyne, 1-tolyl-ll, 13-tetrakosadiynsulfonsyre and l-cyclobutyl-16,18-oktatriakontadiynfosfonat.

20 · ''

Such coatings of 2-dimensional ordered phase may be prepared by

Langmiur-Blodgett method which involves dissolving the polyacetylenic compound in a water immiscible, relatively low boiling solvent and spreading the resultant 25 to the solution as a film on an aqueous surface, preferably a water surface, the water / air interface. The solvent is then evaporated and a layer of molecules of the polyacetylene compound on the aqueous surface remains. Layer of molecules is then 50 compressed to a surface pressure consistent with the formation of a monomolecular layer of the polyacetylenic compound at the water / air interface and conducive to transfer of the monomolecular film to a solid substrate by passing the substrate through the surface. 35 dipping procedure is repeated as desired to build-up additional monomolecular layers of polyacetylenic. film. to a desired thickness of up to about 10 micrometers on the substrate.

18 #

For purposes of this invention it is preferred to employ a multilayered substrate for the polyacetylenic layer 1 the imaging medium. When such an imaging medium 5 is used, it essentially contains a separate conductive layer underlying the polyacetylene imaging layer and may also contain separate support and adhesive layers. In certain applications, where the polyacetylene binder has sufficient integrity at exposure temperatures, the imaging film 10 consist solely of crystals suspended in the binder which forms a single layer base film as the imaging medium.

A typical film for the purpose of this invention comprises microcrystalline polyacetylene in a non-solvating binder 15 or a two-dimensional ordered multilayer phase of polyacetylenes to form a layer having a thickness of about 0.25 to ca. 500 micrometers, preferably from about 2 to ca. 10 micrometers, overlying a substrate with a thickness of ca. 0.013 to ca. 0.25 mm.

20 Supports suitable for the present invention purpose include any of those commercially availabl Em- generally comprises an electrically conductive layer having a thickness of approximately omellom 0.001 wt 0.25 microns, preferably 1:25 thickness between 0.01 and about 0.05 micrometers.

Although transparent conductive layers of up to about 0.05 micrometers is most preferred, opaque conductive layers of up to 5 micrometers can also be used as needed. It ju conductive layer limits the capacitance of the ladningsmot- accepting layer, namely the image-receptive polyacetylenic crystals dispersed in binder or the multilayered 2-dimensional ordered multilayer film of the polyacetylenic compound, and typically has a resistivity of 10 ^ ohms / -55 square or less and preferably 104 ohms / square unit or less. The conductive material is an electrically conductive metal, metal oxide, metal alloy, metal halide 19 or carbon black which metal, metal compound and carbon black components may or may not be suspended in a dispersion medium such as gelatin, dextran, a cellulose ether or ester or any other 5 conventional suspension medium. Suitable metals include gold, silver, platinum, copper, iron, tin, aluminum, indium, nickel, palladium, rhodium and mixtures thereof, as may occur in alloys and metal oxides or halides. A specific metal oxide which may be suitably employed are 10 indium-tin oxide. Silver bromide and copper iodide are representative of the metal halides which may be used as the conductive layer. Of these conductive materials, indium-tin oxide is most preferred.

15 If desired, the polyacetylenic layer may be more firmly to the conductive layer by means of a thin adhesive layer having a thickness of between about 0.1 and 1.5 micrometers. When used, suitable adhesives include acrylate based polymers and copolymers, particularly those containing carboxylate groups 20 such as acrylic acid or methacrylic acid and mixtures of these polymers or copolymers with gelatin.

In certain cases, when a conductive metal sheet used as the substrate, a separate conductive layer may be eliminated and the image-receptive layer 25 is placed directly on the metal sheet conductive support.

The conductive layer is usually supported by a substrate having a thickness of between about 0.0063 and about 2.5 mm for 30-preferably 0.013 to 0.25 mm. Suitable materials employed as substrates include polyester, polyethylene terephthalate, glass, clay-sized paper, fiberboard, metal sheeting, glazed ceramic, cellulose acetate, polystyrene, polycarbonates or any other conventional j5 carrier.

am 20

The substrate or support can be flexible or rigid, opaque or transparent depending on the film finally formed. Particularly preferred are the commercial polyester substrates such as MYLAR (polyethylene terephthalate), 5 supplied by EI duPont Corporation and HOSTAPAN supplied by American Hoechst.

After the supported polyacetylenic film is formed, a leuco base imaging layer is applied over the polyacetylene 10 cal layer. The leuco base layer is prepared by dissolving the leuco dye precursor compound in an inert solvent or mixture of solvents, including acetone, methyl ethyl ketone, dioxane, ethanol, butanol, dichloromethane, cyclohexanone, tetrahydrofuran, carbon tetra-15 chloride, cellosolve, methyl cellosolve, toluene , dichlorobenzene, etc., and mixing the resulting solution with a solution of the halogenated polymeric binder in any of the foregoing inert solvents or mixtures of solvents. The selected 20 leuco dye precursor uniformly distributed throughout the binder layer is incorporated at a concentration between about 1 and ca. 25 weight percent, preferably between about 5 and ca. 15 percent by weight with respect to binder. Coating solutions prepared in this manner are then individually coated in a 25 or more successive layers on the supported polyacetylenic film and dried at a temperature between about 15 and ca. 125 ° C under atmospheric pressure for a period of from about 10 seconds to about 5 hours. Taken together comprises first and second imaging layers describe a lamina having a thickness of between about 1 and ca. 13 J0 micrometers disposed on the conductive substrate. In certain cases, eg. which uses a thin surface layer, a somewhat thicker second layer, e.g.. between about 4 and about 8 micrometers. Movies containing 3 or more layers can be used in thicknesses of up to approximately 20 micrometers or more. The resulting film 35 is placed in a specimen holder below the source of radiant energy for separatlageksponering and fargefrem- 0:21 Calling of a specified image or pattern to be transmitted therein.

In general Having described the invention reference is made 5 to examples which describe preferred embodiments thereof.

EXAMPLE 1

Preparation of a photo-reseptlv film that firmly suspended, uniformly spaced polyacetylenic crystals.

10 - L.et''bege.rglass-b'le the op'pløstr: 15: g pentacosa-10 ^ l ^ -dlynoin- acid at 38 ° C in 45 g of ethyl acetate to form a solution, solution A. A another solution, solution B, was prepared by dissolving 15 g of photographic gelatin in 250 g of 15 water and 30 ml of an aqueous solution containing 3 wt-56 surfactant Gafac RS-7101. Solution B was heated to 40C and introduced into a Waring blender with a capacity of 0.95 liters. Under high speed mixing solution A was added to solution B over a 30 second period 2o. Mixing was continued for an additional 2.5 minutes before pouring onto a stainless steel tray where it was allowed to chill set. The gelled dispersion was cut into approximately 1 cm cubes and placed in an airstream to remove ethyl acetate by evaporation. After the ethyl acetate was 25 removed, the gelled dispersion reconstituted by melting at 40 ° C and adding sufficient water to replace the weight loss that occurred during drying. The crystal size was between about 0.05 and ca. 0.22 micrometers. The reconstituted dispersion was then frozen at about

30 -15 ° C for a period of 2 hours and allowed to warm to room temperature, after which it was melted and coated at a thickness of about 10 micrometers on a 0.1 mil film base, SIERRACIN INTREX-KS2; a polyester base carrying an indium-tin oxide conductive

55 1:01 acid phosphate ester of nonylphenol supplied by GAF

Corporation 2 supplied by Sylmar / SIERRACIN Company 10:00 p.m. t coating, having a resistivity of about 108 ohms / square, which had been overcoated with a 1 micrometer thick layer of an adhesion-promoting material comprising 50 weight percent gelatine and 50 weight percent of a latex polymer. The coated film got 5 to dry in air at ambient temperature yielding an image receptive layer 5 um thick. This film was designated Sample A.

EXAMPLE 2 10 There was prepared a solution containing 2.5 g of polyvinylchloride, 0.3 g of the leuco base p, p ', p "-tris (aminophenyl) carbinol, 50 g of tetrahydrofuran and 10 ml of acetone. This solution was intimately mixed and coated with a wire wound rod over the imaging layer of the film of sample A, example 1 and 15 dried at 115 ° C for 45 seconds to provide a film having two distinct contiguously disposed imaging layers with the leuco base containing layer as the surface. the thickness of this surface layer was 3 micrometers. This film was designated sample B.

20 EXAMPLE 3

Examples 1 and 2 was repeated except that the leuco base imaging surface layer has a thickness of only 1.0 micrometers. The multilayer film of this example are designated 25 Sample C.

EXAMPLE 4

The imaging film, Sample B, prepared in Example 2 was placed in the sample holder of an electron beam recording 3 "streringsapparat and a beam of 15 KeV electrons was employed to expose a set of alphabetic characters in the sample leuco base surface layer. An exposure dose of about 10-5 coulombs / cm2 was used. A second exposure was made using a 20 KeV beam of electrons at 1:35 dose of 8.10 coulomb / cm2 to draw a set of numeric characters in the lower, polyacetylene containing, imaging layer. When the first film was inspected after the exposure was #% 23 undertaken, it was observed clear, well-resolved images of the two character sets. The alphabetic characters were rendered 1:01 clear deep rose pink color, and the numeric characters were a clear deep blue color.

5 EXAMPLE 5

The exposure procedure 1 Example 4 was repeated using another film portion of Sample B except that both exposures were made using a 15 KeV electron beam. 10 Resultatet.fra this experiment was a picture of the alphabetic character set in a clear deep rose pink color, but it was No representation of the numeric character set. Even when the exposure of the numeric character set is made at a dose of 10 "7 coulomb / cm², it could not be seen any image. This experiment demonstrates that 15 at low doses, i.e. less than about 7.10 C / cm2 of 15 KeV electrons, is the leuco dye containing layer is insensitive to exposure.

Furthermore it also demonstrates that a 15 KeV beam of the electrode 20 sits will not give an image in the lower, polyacetylene containing, layer since the electrons can not penetrate beyond the surface layer 3 prneter thickness. The expected range of 15 KeV electrons in this layer is approximately 2.8 micrometers.

25 EXAMPLE 6

The exposure procedure of Example 4 was used to obtain images of the alphabetic character set and the numeric character sets the Sample C film of Example 3. The results of this experiment, a clear blue image of the numeric characters and very 30 dark blue image of the alphabetic characters. The interpretation is that the 15 KeV beam that was used. to produce the alphabetic set has penetrated in a thickness of the leuco base surface layer exceeding 1 micrometer and has exposed the lower, polyacetylene layer. 35 Since the dosage is relatively high, the resulting image is dominated by the blue color of the lower imaging layer. This experiment demonstrates the criticality of choosing 24 ft a combination of surface layer thickness and beam energy such that an image can be created exclusively in the surface layer to the exclusion of the lower layer where the electrons can not penetrate.

5 EXAMPLE 7

There was prepared a solution containing 2.5 g of polyvinylchloride, 50 g of tetrahydrofuran and 0.3 g of the leuco carbinol base of malachite green. This solution was intimately mixed and 10 coated with a wire wound rod over the imaging layer of the film of Sample A and dried at 75eC for 2 minutes to provide a film which had two distinct contiguously disposed imaging layers, the leuco base containing layer as the surface layer . The thickness of this over-15 surface layer was 3 micrometers. The film was designated as Sample D.

EXAMPLE 8

The procedure of Example 4 was employed to expose a strip of the film of Sample D. Alphabetic characters were exposed with a 15:20 KeV beam at about 10 "® coulomb / cm2. Numeric characters were exposed at a dose of approximately 10" ® coulomb / cm2 with a 30 KeV beam. Clean, clear, well-resolved images of the character sets were obtained. The alphabetic characters had a deep green color and numeric characters a deep blue color. The exposed film was designated 25 sample E.

EXAMPLE 9

The exposed film of Sample E was briefly heated to about 70 ° C whereby the blueness of the numerals were changed permanently j0 to a clear, well dissolved orange yellow image. The green image of the alphabetical characters remained unchanged. This exposed film was designated as Sample F.

EXAMPLE October 35 The exposed and heated film of Sample F was returned to the holder in the electron beam exposure apparatus and 20 KeV of electrons was employed to expose a series of small "25 geometric figures at a dosage of about ΙΟ - ** coulomb / cm2. When exposed film was inspected, it was observed clear, well resolved, clean images in three different colors.

A set alphabetic characters in green, a set of characters in the orange-yellow 5 and a set geometric figures in a deep color.

EXAMPLE 11

The film of Sample B was placed in the electron beam exposure device and a 15 KeV beam of electrons was used 10 to form an image of a set of geometric figures at a dosage of about 10 '^ coulomb / cm2. This image was seen to have a clear, deep rose pink color when the sample was removed from the exposure apparatus. - '15 Another image was now generated by exposing the film to a source of ultraviolet light, predominantly below 300 micrometers in wavelength, through a stencil mark bearing alphabetic characters. Since the lower, polyacetylene layer is far more sensitive to ultraviolet light than the leuco dye No. 20, the alphabetic character set rendered in a clear deep blue in sharp contrast to the geometric shapes in pink pink color as exposed by the electron beam in leukofarge drug-surface layer .

25 It will be appreciated that many modifications and alterations in the foregoing examples will be apparent from the foregoing. Eg. can any of the other beam sources for charged particles used in the examples for the electron beam when employed at dosage levels are 5 "equivalent in effect to the above electron beam dosage levels.

The present invention also includes the use of a recording film comprising a conductive material 35 supporting three or more individual and superimposed imaging layers, each composed of a binder containing a dissimilar photosensitive compound R '26 may produce distinguishable hue or color and to 1 image said imaging layers employing separate and distinct beam energies, each modulated to penetrate the individual imaging layers. Especially five desired of these is such registreringsfllm having three separate superimposed imaging layers, two of which contain different polyphenylmethane dye precursor compounds, or two containing different poly-acetylenic compounds, which are developed individually to 10 that display distinctive portions of the transmitted information in several colors that can be distinguished from each other. In this case, progressively increasing beam energies within the range of a. 1 to 50 keV for the imaging layers. In a broad sense, a plurality of such superimposed layers, 15 each containing a distinctive photosensitive compound, may be regarded as forming a composite surface layer of the present registreringsfllm.

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