DE2736098A1 - PROCESS AND MATERIAL FOR THE DEVELOPMENT OF IMAGES - Google Patents

Description

-JK

Company DAI NIPPON INSATSÜ KABUSHIKI KAISHA, 12, Kaga-Cho 1-Chome, Ichigaya, Shinjuku-Ku, Tokyo-To , Japan

Process and material for developing images.

The invention relates generally to techniques for developing more visible Images using so-called silver-free photosensitive Materials or photosensitive materials containing compounds other than silver salts. In particular the invention relates to a method of developing visible images having excellent contrast and high sensitivity by treating an image developing additive which is a polyacid of molybdenum or tungsten or their salts or complexes The invention also relates to an image developing material for this method.

It is known that heteropolyacids and the like of molybdenum and tungsten such as phosphomolybdic acid by light or

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Heat can be reduced and produce colors that range from blue to black. Investigations have also been carried out to take advantage of this phenomenon to develop images using flash. At one known for this purpose Technology becomes a heat-sensitive one on a reflective original Material formed by applying phosphomolybdic acid, for example as a coating on a transparent base, and there is a flash light through this heat-sensitive material projected through onto the reflective original, and there will be Heat rays from the black parts of the reflective original applied as radiant heat to the thermosensitive material, thereby creating an image in the thermosensitive material will. However, a number of practical difficulties arise with this method. For example, the resolution or the Resolving power down, due to the heat diffusion towards the edge of the picture, and only materials can can be used as a carrier that are transparent and also have a low thermal conductivity. (U.S. Patent 2,980,551).

GB-PS 1,008,537 and US-PS 3,285,746 also disclose the projecting of intense rays of light, the energy of which exceeds a certain threshold, onto a film made of a solid solution of a poly acid such as phosphomolybdic acid or Silicon tungstic acid and a polyvinyl alcohol / acetate polymer or polyvinyl butyral, which makes the film opaque. From the teaching of these patent specifications it can be seen that that the above material can be used as a photographic material capable of producing an image

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bring when it is irradiated by intense, image-like rays of light will. However, since it is necessary to continuously supply image light rays with a high one required for the process Projecting intensity (due to the low sensitivity) is the usefulness of the material as a photographic material small amount.

Studies of coloring or color developing property of compositions such as phosphomolybdic acid have shown that this coloring involves two stages of the process.

Specifically, in the first stage, phosphomolybdic acid or the like is reduced and is sometimes slightly colored. In the case where this coloring is extremely slight, the image may be a latent image. This primary coloring is achieved by the reduction of phosphomolybdic acid or the like as heretofore known, and for this purpose one can Make use of a method in which the phosphomolybdic acid in the simultaneous presence of a reducing By means of irradiating with ultraviolet rays, or by a method in which a reducing agent with the phosphomolybdic acid is brought into contact.

In the second stage, the phosphomolybdic acid, which has been subjected to the primary coloring described above, is absorbed Light and takes on a dark or black color. An important point is that this second stage is not through irradiation only

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can be continued with ultraviolet rays, but that progress can only be made through the use of light rays can be achieved that have a longer wavelength than the ultraviolet range (visible and infrared rays). While light with a long wavelength of this type has a color darkening effect on the phosphomolybdic acid which has been subjected to the primary coloring, it has none at all Effect on phosphomolybdic acid which has not been subjected to primary coloring. The property of phosphomolybdic acid is not limited to this acid only, but it occurs in general with polyacids of molybdenum and tungsten and of salts and complexes of these components as described below.

Further studies are based on the above findings been executed. As a result, an image developing method of high sensitivity has been developed under Use of silver-free materials and an improved photosensitive material suitable for use therein Procedure is suitable.

The invention consists - briefly summarized - in an image development process, which is characterized by the following steps:

1. Reduction in the form of an image, i.e., discoloration of an imaging agent composed of polyacids of molybdenum and tungsten and

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Salts and complexes of these polyacids, which is provided in layer form on at least one surface of a support;

2. Irradiation of the entire surface of the layered surface that produces an image By means of including colored parts and still uncolored parts with light rays of great wavelength, which only are absorbable by the colored parts, so that a colored image is produced in which the optical density is only colored parts is increased to an unusual degree. For the most part, the picture is a black picture, however are also pictures with a brown tone or other tones, depending on the means forming or developing the picture possible. These images are hereinafter referred to as "black images".

The image development process according to the invention considerably simplifies the coloring process step (ie the first process step) in which the coloring takes place in the form of the image and which determines the photosensitivity of the finished material which forms or develops the image. In the case where this step is carried out by irradiation with light, only an extremely short exposure time is sufficient (this time varies with the composition, but is of the order of 100 mJ / cm ^a for satisfactory results.

The second step is the total extension of the image forming Medium-bearing surface including the primary colored

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Parts of the image are irradiated with light rays of great wavelength, to which the as yet uncolored parts are not sensitive, whereupon only the image parts are selectively colored black. That is, in second step is a contrast similar to that

obtained due to exposure to image pattern light rays, and only by irradiating the entire surface / without a controlled exposure to image-like light rays must make. This means that the entire surface irradiation with the long-wavelength rays of light has not only a developing effect but also an effective one As a result, an effect of increasing the sensitivity of the image forming agent is achieved. As a result, when an assembly comprising a substrate provided with a layer of the image-forming agent, is used as photographic material, the second process step is completely separated from the first process step, this arrangement becomes an extremely high sensitivity material in which the contrast after the second step is effected, the imagewise exposure taking place only in the first step.

The material of the base is not limited, and once the image-forming material has been produced, it is possible to control the entire image formation or development process without performing wet treatment, whereby a black image with excellent resolution can be advantageously obtained.

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According to the invention, there is provided an improved non-silver photosensitive Material created. In a conventional photosensitive material comprising a base and a layer of one an image developing material, such as a polyacid of molybdenum or tungsten, which is applied as a layer on at least one surface the substrate is provided, a color change of the image-forming agent due to the absorption of a considerable Heat quantity causes, regardless of whether the heat is supplied in one stage or in two stages. For this reason this absorbed heat causes an increase in undesirable results such as the occurrence of cracks and pinholes in of the surface of the layer of the image forming agent, powdering of the layer and spreading by infiltration the black parts into the non-image parts. These disturbances reduce the resolution of the picture and the durability of the picture, which is why these disturbances should be eliminated in practical use.

It has been found that when using a film of transparent polymer substance on the layer of the image-generating

all these disadvantages can be avoided / and it means it also improves the stability of the final photosensitive or image-forming material itself.

In particular, the present invention will produce an improved image Material created that consists of the following parts:

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a) a document;

b) an image-forming layer on at least one surface of the support, the image-forming agent being composed of polyacids consists of molybdenum and tungsten and salts and complexes of these polyacids,

c) a transparent polymer film on the image-forming layer, at least one of the image-forming layer and the transparent polymer film contains a reducing agent.

The nature, use and other features of the invention will emerge will emerge from the following description, which begins with a consideration of general aspects and details of the invention and followed by specific practical examples relating to preferred embodiments of the invention. In the Drawing shows:

Fig. 1 is a partial view of an example of a basic photosensitive Material in a cut that can be used for the invention.

Fig. 2 is a similar sectional view showing an example of an improved photosensitive material according to the invention shows, and

Fig. 3 shows similar sectional views to explain the figures and 4:

Procreation according to a two-step process according to the invention.

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The imaging or development process of the invention can be carried out by using an image-forming photosensitive material having a construction as shown in FIG Fig. 1 is shown. This material contains a base 1 and a layer 2 of image-forming material, which in addition to the image-forming agent, a binder and / or a reducing agent Contains funds.

The basic construction of an improved imaging material according to the invention is shown in FIG. This material consists of a transparent polymer film 3 on the outer surface of the layer 2 of image forming material (Fig. 1). In this case, at least in the layer 2 of image-forming material or in the transparent polymer film 3 there is a reducing one Funds included.

The base 1 can consist of any suitable material, such as paper, plastic film, glass, metal or the like, and it can be of any suitable shape, provided that at least one surface is present.

The image forming agent according to the invention can be made from polyacids (Isopolyacids and heteropolyacids) of molybdenum and tungsten and salts (preferably alkali metal salts and ammonium salts) and complexes of these acids. Preferred examples of these Suitable imaging agents are molybdic acid, sodium molybdate, Ammonium molybdate, phosphomolybdic acid, ammonium phosphorus

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molybdate, silicon molybdic acid, ammonium silicon molybdate, Arsenic molybdic acid, ammonium arsenic molybdate, sodium arsenic molybdate, tungstic acid, ammonium tungstate, phosphotungstic acid, ammonium phosphotungstate, Silicon tungstic acid, ammonium silicon tungstate, Sodium Silicon Tungstate, Arsenic Tungstic Acid, Ammonium Arsenic Tungstate, Sodium Arsenic Tungstate.

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In addition, compounds such as complexes with amines such as isopropylammonium molybdate and complexes with other metals such as phosphorus vanadium molybdic acid can be used.

While the aforementioned molybdic acid, tungstic acid, and the salts of these acids are used with the intent that Not to include ortho-acid and its salts, the ortho-acid and its salts can be in the primary starting material must be contained since they exist as an isopoly acid or a salt of this acid in an acidic state.

Usually an image forming agent of this type is called Coating applied, namely as an aqueous or alcoholic solution together with a binder or in addition with a reducing agent as described later. The coating is applied to the substrate 1, and it

Image-generating layer 2 is present after drying. As a result, a polymeric compound that is in water or is soluble in an alcohol, such as gelatin, polyvinyl alcohol, polyvinyl butyral and cellulose esters, preferably as a binder

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used . However, other film-forming polymers can also be used as a coating in the dispersed state in the presence of a suitable emulsifier can be applied.

In addition to water and alcohols, solvents that can dissolve the image-forming agents, such as acetone, methyl, Ethyl, ketone and dimethylformamide can be used.

Examples of reducing agents _for which the invention may be used in accordance are organic reducing agents, such as D-glucose, thiourea, Oxalatoeisen, Michlersketon, L-ascorbic acid, diphenylamine, diphenylcarbazide, and polymers such as polyvinyl alcohol, polyvinyl acetate and polyvinyl butyral, and inorganic reducing agents such as titanium oxide, zinc oxide, tin chloride, and metals such as lead, tin, iron and zinc. The reducing agent; however, it is not limited to the compounds enumerated above, but any suitable substance can be used provided that it has a reducing effect with respect to the above- described image-forming agent.

Of these reducing agents, those with poor reducing ability, such as D-glucose and polymers, do not give enhancement of coloration only in cooperation with the image-forming agent. As a result, these reducing agents can be left in the image forming layer 2 in a mixed state. In addition, these polymeric compounds can also

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Have the effect of the above-mentioned binder.

Of the polymers, those like nitrocellulose do not themselves have a reducing effect while acting as binders can be used. Regarding a particular polymer or the like, determining whether it is the desired one can be made has a reducing effect, can be made in the following manner. A film (about 10 µm thick) made with a weight ratio of 1 of the test substance to 2 of the phosphomolybdic acid is provided on a polyester film, which has non-reducing property, and the film becomes exposed to ultraviolet rays for one hour Irradiated from a distance of 20cm using a 25OW mercury lamp. If the difference in Macbeth optical diffusion transmission concentrations of the film before and after irradiation exceeds ~ 0.01, this test substance can be used as a reducing agent Agents according to the invention can be used.

On the other hand, when strongly reducing substances such as thiocarbamide, Oxalato-iron, L-ascorbic acid, diphenyl «^ min, diphenylcarbazide and Michler's ketone contained in the image-forming layer 2, they cause fogging. So if this strongly reducing substances should be included in the arrangement of the image-forming material, they should be in the Polymer film 3 (hereinafter referred to as "coating layer") may be contained.

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As the polymer for forming the coating layer 3 in the improved image-forming material, any material can be used, that is transparent and that can be applied as a layer. If the binder of the image-forming layer 2 is used When using polymer which is soluble in water or in an alcohol, it is desirable as that of the coating layer forming polymer to use one which is insoluble in water or in an alcohol. The reason for this is to prevent that the image-forming layer 2 once formed dissolves and that a disturbance of the intermediate layer between the image generating layer 2 and the coating layer 3 when using the polymer forming the coating layer in the form of a solution results. In many cases, the image in the image-forming layer 2 is located near the intermediate layer between it and the Coating layer 3 is formed, and it is the prevention of interference of the intermediate layer for the enhancement of the resolving power important.

Another reason is that when using a solvent, which can dissolve the image-forming layer to form the coating layer if a strong reducing agent Contained in this solution, the image-forming layer is dissolved and at the same time a coloring when the Solution is caused on the image-forming layer. Examples of preferred polymers for forming the coating layer are

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Polyvinyl chloride resins, polyvinyl acetate resins, polyvinylidene chloride resins, Cellulose resins, polystyrene, polypropylene, polyvinylcarbazole, methacrylic resins, polyamide resins, polyurethane resins, fluororesins and rubber chlorides. Polyvinyl chloride resins and polyvinylidene chloride resins also function as reducing agents.

A representative process for the manufacture of imaging Materials based on the above-mentioned starting ma-

is
materials / described below.

First, the imaging agent is dissolved in water or in an alcohol and, if necessary, further becomes a binder and / or a weak reducing agent additionally dissolved in the solvent. The solution thus obtained is applied as a layer on the base 1 and dried in air so that the image-forming layer 2 is formed.

If a permeable paper is used for the base 1, it can additionally have a reducing effect and the effect have a binder. For this reason, the combined structure of the base 1 and the image-forming layer 2 according to the invention can be prepared by applying the imaging agent directly without using a additional binder and / or a reducing agent.

However, it is the use of a binder in the solution of the above-mentioned image-forming agent for image formation and preferable to solution for coating properties. If a binder is used, it is preferred Concentration used that the concentration of the imaging

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the agent in the image-forming layer is greater than 15% by weight in the dry state in order to give the image a high optical density to rent. Further, it is preferable that in order to improve the film properties To maintain the imaging layer in good condition, the concentration of the binder in the dry state Is 10 to 60 wt%. When the image-forming layer 2 contains a reducing agent, the amount used depends on the reducing power of the reducing agent, but adjustment of the reducing agent is required, wherein the amount is small for a relatively strong reducing agent and for a relatively weak reducing agent Medium is slightly larger. In any case, the appropriate amount of the reducing agent is determined in a range in which the image-forming layer does not acquire any substantial color when irradiated with light rays other than ultraviolet rays contain.

For example, if D-glucose (a relatively weakly reducing Agent) is used in combination with a phosphomolybdic acid is a concentration of D-glucose in the image-forming layer in the dry state from 5 to 50% by weight.

Furthermore, when the reducing agent additionally acts as a binder, as in the case of the above-mentioned polymeric reducing agents Is the case, the concentration range of the binder can be used immediately.

The thickness of the image-generating layer on the base 1 should be in the order of 2 to 20 μm. When these di-

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ke is less than 2 μm, the image density tends to be poor. On the other hand, if the thickness exceeds 20 μm , the density before exposure (ie, the density of non-image parts) increases. For this reason, there is a tendency that the contrast of the image becomes weak.

An image forming material as shown in Fig. 1 is obtained.

An improved imaging material according to the invention is made by having the coating layer described above forming polymer is applied to the imaging layer 2 of the imaging material shown in FIG. For this layer, the polymer forming the coating layer is preferably dissolved in a solvent which is the image-forming polymer Agent and the binder does not dissolve. If a binder soluble in water and alcohol is used in the imaging Layer is used, the coating layer forming polymer is in an organic solvent with proportionately low solubility in water and alcohol, for example benzene, toluene, tetrahydrofuran, dissolved, and it will - if required - a reducing agent is added and the resulting mixture is applied as a layer over the image-forming Layer 2 applied. If the reducing agent used in this process is insoluble in the solvent, the reducing agent is dispersed as a fine powder in the binder solution using an ultrasonic dispersion machine, and then the resulting dispersion is coated onto the imaging layer 2 upset. The solvent is then dried in a

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Evaporated in a stream of air, whereupon the coating layer 3 obtained will.

It has been found that a thickness of the coating layer 3 on the order of 5 to 15 µm is desirable. If the Thickness is less than 5 µm, the effect of the picture part may be cannot be neglected, and the effectiveness of the coating layer is poor. On the other hand, when the thickness is 15 µm

effect

exceeds, the light-absorbing / the image-generating Layer 2 bad and it takes away the sensitivity of the arrangement as a photosensitive material.

For applying the solution or dispersion of the above The imaging agent on the base or the coating layer forming agent may be any known one Methods such as bar coating, roller coating, dip coating, spray coating, etc.

The improved image-forming material of the present invention, the has been prepared in the manner described above can take the following three arrangements of reducing agent, depending on its presence in the image-forming layer 2 and the coating layer 3.

a) The reducing agent is contained in the coating layer 3;

b) the reducing agent is in the imaging layer 2 included;

c) the reducing agent is contained both in the coating layer and in the image-forming layer 2.

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In each of the above three cases, the improved imaging Material according to the invention fully exhibits the highly desirable properties mentioned above. That is, it is the occurrence of various defects such as cracks, pinholes in the surface of the image-forming layer 2, powder formation on the surface and infiltration of the image parts into the image-free parts, effectively eliminated, and other effects, such as an improvement in the resolution of the image and the preservability of the image and the preservation stability of use achieved.

However, differences are found in the following points. The above case b) corresponds to an arrangement in which an overcoat layer on an image-forming layer a conventional photosensitive material is provided, but is with the same reducing power of the reducing agent the sensitivity in case a) is somewhat lower than in case b). However, the case a) is advantageous in that a strong reducing agent can be used and the prevention of fogging is better. In this case results there is also a great advantage in that the formation of a coating layer containing the reducing agent a short time before the photosensitive material is used, the preservability of the image-forming material is considerable can be improved. The sensitivity in case c) increases by twice that in case b).

The imaging or developing process of the invention and the application of the imaging material thus obtained will now be described. This

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Procedure contains two procedural steps.

In the first step, the layer 2 is made of image-forming material, which is provided on the base 1, reduced image-like, so that colored parts are obtained. This coloring can can be achieved by one of two methods. In one of these processes, when coating layer 2 of image-forming Agent on pad 1, the reducing agent is present at the same time (including both cases in which the reducing agent is contained in the image-forming agent layer 2 and in the case where it is in the overcoat layer 3 is included), and it is the surface of the image-forming layer 2 on the base 3, which is thus obtained is irradiated with imagewise ultraviolet rays. In the other staining process, the reducing agent is caused to The surface 2 made of image-generating material can be immersed in a picture-like manner To touch means on the pad 1. Of the reducing agents listed above, a strongly reducing agent is used, such as tin chloride is dissolved in a solvent such as water and becomes a binder if necessary added to cause a conversion to color, which is sprayed onto the required image parts by the paint spraying process will. By this method, a reduction coloring in the image form on the surface 2 is made of image-forming Means (Fig. 1) obtained.

The first dyeing process is a particularly interesting process, and, while the use of the imaging material shown in Fig. 2 is preferred, it is possible

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that in Fig. 1 material shown.

As shown in Fig. 3, which shows the case in which the image forming material shown in Fig. 2 is used, image-like ultraviolet rays are transmitted through the coating layer 3 of the photosensitive material onto the outer surface of the image forming layer 2 (or the intermediate layer between the layer 2 and the coating layer 3, which intermediate layer or which outer layer is hereinafter referred to as the "image-forming surface"). With a radiation energy of the order of magnitude of 100 mJ / cm ² , a primary coloring part 4 with a light blue color with the image pattern on the image-forming surface is achieved.

The term "ultraviolet rays" is used herein to refer to rays of light that emit light at the wavelength of the ultraviolet range and which can also contain visible light and infrared light. As a light source, which emits the imagewise ultraviolet rays may be a mercury lamp, a xenon flash lamp Laser beam or any other light source can be used. When these ultraviolet rays pass through a transmission original 5 imagewise ultraviolet rays can be obtained. Laser light can be projected imagewise as a direct beam will. Ordinary camera photography is also possible, but in this case it is of course necessary that the light radiation projected onto the lens contains ultraviolet rays.

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In the second step, the entire image is generated Surface including the colored parts and the as yet uncolored parts obtained in the manner described above are irradiated with light rays of great wavelength, which is not noticed by the as yet uncolored parts, so that only the the above-mentioned colored parts are sharply colored in black or with a dark color, whereby the image part 6 is obtained will. Figs. 3 and 4 show the case where the image forming material shown in Fig. 2 is used. The same Description also applies to the case in which the coating layer 3 is not present, so in which the material according to FIG. 1 is used.

It is necessary that from the above-mentioned long-wave radiation all short-wave light rays that pass through the still uncolored parts can be absorbed, separated. The critical wavelength that meets the conditions only to be absorbed by the colored parts and not to be absorbed by the as yet uncolored parts is at different combinations of the image-forming agent and the reducing agent. But it has been shown that this critical wavelength is generally in the vicinity of the boundary between the range of visible light and the area of ultraviolet light. This long-wave light can be obtained by applying the light from a light source, such as a xenon lamp, a tungsten lamp, a xenon flashlight or a laser device, a filter penetrates, that cuts off the ultraviolet rays.

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By irradiating this stage, the density of the colored parts increases as the amount of light absorbed by these parts increases, whereby the colored parts become almost pitch black while the uncolored parts experience almost no change. As a result, the exposure at this stage can be selected within a certain range according to the required contrast, but a satisfactory contrast can be achieved ^{even with a minimum exposure of the order of magnitude of 2.5 J / cm 2.}

The black image thus obtained has a contrast with a degree of clarity which cannot be achieved with a conventional silver-free photosensitive material. Even if the material is left as it is, no color change occurs, and the non-image parts also do not turn black. However, in order to obtain an image that is stable even when heated and irradiated with ultraviolet light, it is preferable to use a To perform fixing treatment. In detail, according to the invention the uncolored imaging agent remaining in the non-image parts may cause its imaging ability by treatment with an alkaline substance such as ammonia gas, ammonia water or an aqueous solution of sodium hydroxide to lose. An image treated in this way has a high contrast and the material retains its coloring even when heated, whereby the color of the non-image parts is not changed either.

Another notable feature is that the alkaline Treatment not only after the production of the black

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image is effective, but also when the entire surface of the image-forming agent is treated after the primary coloring will. When the surface of the image-forming agent after primary coloring with an appropriate alkali concentration treated for a suitable time (e.g. 2-3 seconds in NH ^ gas) becomes, the uncolored parts lose their image-forming ability, but the image parts that have been colored once do not lose their ability to turn black and are selectively black when exposed to long-wave light rays to be colored.

The above-described image-forming method and material according to the invention can advantageously be used in various Systems such as high-speed reproduction systems, projection imaging systems, and systems for the production of IC masks. In such applications, the operating characteristics of these systems are considerably improved, because of such advantages as high image density, high resolution, high sensitivity and good Protective stability of the imaging material before and after exposure.

In order to show more clearly the nature and applicability of the invention, the following practical examples are described which are preferred embodiments of the invention.

In the following examples, the amounts given in “parts” and “percent” are to be understood as parts by weight and percentages by weight.

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example 1

One part of phosphomolybdic acid was divided into five parts of a 10% strength dissolved aqueous polyvinyl alcohol solution, and it was the resulting solution with the help of a wire bar on a Polyester film applied, followed by a photosensitive Arrangement with a layer of image-forming material with a thickness of 8 μm was obtained.

It was a transfer original in direct contact with the thus obtained photosensitive assembly brought through the original during an exposure time of 10 seconds was exposed using a 500 watt ultra-high voltage mercury arc lamp from a distance of 30 cm, whereupon an image was obtained in which the exposed Parts had turned blue.

The transfer original was then removed and it became the entire surface of this exposed photosensitive arrangement with light from a xenon flash lamp (RISOTRAPEN UP TU-207, manufactured by Riso Kagaku Sha, Japan), the light having passed through a filter to cut off ultraviolet rays (Toshiba AT-V-Y 47). An image was obtained in which only the blue parts, which are the ultra-high voltage mercury

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have been exposed to a silver arc lamp are.

It was found that the optical transmission density of the Parts of the image was increased considerably, from a density of 0.1 before flash exposure to a value of 2.0 after

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the flash exposure. During this time the transmission density remained of the non-image parts to 0.04.

Example 2

One part of the phosphomolybdic acid was dissolved in five parts of a 10% polyvinyl butyral alcohol solution and it was the resulting solution is applied as a layer by means of a wire bar on art paper, creating a photosensitive Arrangement was obtained. Using this photosensitive Arrangement, a black image was obtained by the method explained in FIG.

Example 3

One part of phosphomolybdic acid and one part of D-glucose were dissolved in five parts of collodion, and it became the resultant Liquid used for the dip coating of a glass support or a glass support, whereupon a photosensitive arrangement was obtained. Using this photosensitive assembly, the one described in Example 1 was used Procedure to obtain a black screen.

Example 4

A photosensitive assembly was prepared by the procedure described in Example 1, using instead of Phosphomolybdic acid silicon molybdic acid was used. Using this photosensitive arrangement was made with the method according to Example 1 obtained a black image.

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Example 5

A photosensitive assembly was created by the example 2 prepared method described, wherein instead of phosphomolybdic acid Siliciumunolybdic acid was used. Using this photosensitive arrangement, the Method according to Example 2 obtained a black image.

Example 6

Using a photosensitive arrangement according to Example 3 was prepared, but using instead of Phosphomolbybdic acid When silicon molybdic acid was used, using the procedure of Example 3, a black image was obtained.

Example 7

One part phosphotungstic acid was divided into five parts of a 10% strength Polyvinyl butyral alcohol solution dissolved and it became the resulting solution is applied as a layer to a sheet of art paper, using a wire bar, creating a photosensitive assembly has been prepared. This photosensitive Arrangement was exposed by a xenon flash lamp (RISO TRAPEN UP TU-207) through a filter to make it visible and isolate infrared rays, and pass through a transmission original that is in direct contact with the surface the photosensitive assembly was located. An image was obtained in which the parts thus exposed were colored.

It was then removed from the original broadcast, and it became the entire surface of the photosensitive thus exposed

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Arrangement exposed to the light of a xenon flash lamp, through a filter to cut off ultraviolet rays, whereupon an image was obtained in which parts colored blue had turned black.

Example 8

The image obtained in Example 1 was exposed to ammonia gas. This turned the image into a stable image, which was also the case with Heating did not change the color.

Example 9

The image obtained according to Example 2 was immersed in an ammonia solution.

Example 10

A TEiI of molybdic acid was in five parts of a 10% aqueous The solution was dissolved in polyvinyl alcohol, and the resulting solution was brought to pH 2 by adding hydrochloric acid set. The solution was then coated onto a polyester film using a wire bar, see above that a photosensitive assembly was obtained. This photosensitive Arrangement was used to form an image similar to Example 1, whereupon a brown image was obtained became.

Example 11

The method according to Example 10, wherein instead of molybdic acid ammonium molybdate and instead of a 10% aqueous polyvinyl alcohol solution a 10% aqueous polyacrylic acid solution

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was used. The result was a black screen.

Example 12

The method according to Example 10 was carried out, with isopropyl anunonium molybdate, which is made up of, instead of molybdic acid
obtained from the reaction of isopropylamine and ammonium molybdate
became. A black screen resulted.

Example 13

One part of phosphomolybdic acid was dissolved in five parts of a 10% polyvinyl alcohol aqueous solution, and the resulting solution was coated on a sheet of polyester film by means of a wire bar and then dried in an oven at 50 ° C. for five minutes whereupon an image-forming layer was obtained. It was then called
Coating layer a 5% solution of UVoluene of polyvinyl chloride
applied as a coating to this imaging layer with the aid of a wire bar, after which the layer was dried in an oven at 50 ° C. for five minutes. Thus, a photosensitive assembly with a thickness of
13 μm (imaging layer about 8 μm, coating layer about 5 μm).

A transfer original was brought into direct contact with this photosensitive assembly, which was then used during
Was exposed to the light of a 500 watt ultra-high voltage mercury lamp at a distance of 30 cm for 10 seconds, whereupon an image was obtained in which the exposed parts had turned blue. The original transmission was designed

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and the entire surface of the photosensitive assembly thus exposed was exposed to the light of a xenon flash lamp (RISO TRANPEN UP TU-207) sent to the separation of ultraviolet rays through a filter (Toshiba AT-V-Y 47) became. An image was obtained in which only the blue parts of the ultra-high voltage mercury lamp exposed image turned black.

It was found that the optical transmission density of the image parts was increased considerably from one density from 0.1 before flash exposure to 2.0 after flash exposure. During this time the transmission density remained of the non-image parts to 0.04.

Example 14

One part of phosphomolybdic acid was divided into five parts of a 10% strength Polyvinyl butyral alcohol solution dissolved. The resulting solution was coated with a wire bar on a Sheets of art paper applied and then dried in an oven at 50 ° C for five minutes, whereupon a imaging layer was obtained. On this image-generating Layer was applied a 10% toluene solution of ethyl cellulose, whereby a photosensitive assembly was obtained. Using this photosensitive assembly, the procedure of Example 13 was carried out to produce a black image was generated.

Example 15 One part of phosphomolybdic acid was dissolved and divided into five parts

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ORlGfNAL INSPECTED

len of a collodion solution, and it became the resultant Solution applied to a glass substrate by dip coating to obtain an imaging layer. To this In the imaging layer, a 5% polyvinylidene chloride-THF solution was applied as a coating and for five Minutes dried in an oven at 50 ° C to make a photosensitive To create arrangement. Using this photosensitive assembly, the procedure of Example 13 produced a Black screen preserved.

Example 16

A photosensitive one obtained by following the procedure of Example 13 An arrangement using silicon molybdic acid instead of phosphomolybdic acid was made in a similar manner as used in Example 13 to produce a black image.

Example 17

A photosensitive arrangement made according to the method according to Example 14 was prepared using instead of phosphomolybdic acid Silicon molybdic acid was used in a similar manner Manner as used in Example 14 to produce a black image.

Example 18

A photosensitive device, which was prepared according to Example 15 was used in place of phosphomolybdic acid SiIzi ziummolybdänsäure was similar as used in case of game 15 to produce a black image.

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Example 19

One part of phosphotungstic acid was dissolved in five parts of a 10% polyvinyl butyral alcohol solution and it became the The resulting solution is applied as a coating to a sheet of art paper with the help of a wire bar and thus forms an image Layer made. A 5% vinyl chloride resin solution in toluene was applied to this imaging layer, whereby a photosensitive assembly was obtained. This photosensitive assembly was made with the light of a xenon flash lamp (RISO TRAPEN UP TU-207, manufactured by Riso Kagaku Sha, Japan) that had passed through a filter, to separate visible and infrared rays, and which had penetrated a transmission original that was in direct contact with the surface of the photosensitive assembly. An image was obtained in which the exposed to light Partially colored.

The transmission original was then removed and the entire surface of this photosensitive assembly thus exposed became exposed to the light of a xenon flash lamp, which was passed through a filter to isolate ultraviolet rays, whereupon an image in which blue parts were blackened was obtained.

Example 20

One part of a substance obtained from a reaction of isopropylamine and phosphomolybdic acid was divided into five parts a 10% polyvinyl butyral alcohol solution, and it was the resulting solution with a wire bar as loading

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layer applied to a polyester film, whereupon a imaging layer was obtained. It was then coated with a 5% vinyl chloride resin THF solution imaging layer was applied, whereupon a photosensitive assembly was obtained. When using this photosensitive Arrangement, a black image was obtained by the method according to the example.

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Claims (1)

DIPL ING KLAL'S ΒΕ'ΙΓΙ; DIPL-PHYS. ROBERi " MuNZHUbLR *"' PATENT LAWYERS WIDENMAYERSTRASSE 6 U BOOO MUNICH 22 TEL <O89> 22 25 3O 29 91 92 August 10, 1977 A 17077 B / ib / De PATENT CLAIMS 1. A method for developing an image, characterized in that that an imaging agent composed of polyacids of molybdenum or tungsten or salts or complexes of these polyacids reduced in layer form on at least one surface of a base and thereby discolored in the form of an image and that the entire area of the surface of the imaging agent including the colored and as yet uncolored Parts is irradiated with such long-wave light rays that can only be absorbed by the colored parts, so that a colored image is formed in which only the colored parts selectively have considerably increased optical density. 2. The method according to claim 1, characterized in that the image-forming agent simultaneously with a reducing Agent is present on the surface of the pad. 3. The method according to claim 2, characterized in that the imaging agent layer contains the reducing agent. 809808/0756 ~ ² ~ Bankhaus Merck Fmck 4 Co Munich iBLZ 7ΟΟ3Ο4ΟΟ) Account No. ^ 54649 Bankhaus M Aufhdusei Munich No. ^ 6t3OO Postscheck Munich 2Ο9Ο4 ΘΟΟ Telegram address patent senior ORIGINAL INSPECTED ~ ² ~ 2736u'iS 4. The method according to claim 2, characterized in that a transparent one on the layer of image-forming agent polymeric film-containing coating layer is provided and that at least the layer of image-forming agent or at least the coating layer contains a reducing agent. 5. The method according to claim 1, characterized in that the reducing agent is caused to directly the outer Touching the surface of the image-forming agent on the support and thus causing a coloration in the form of the image. 6. The method according to claim 1, characterized in that the imaging agent consists of at least one of the following substances: molybdic acid, sodium molybdate, ammonium molybdate, Phosphomolybdic acid, ammonium phosphorus molybdate, silicon molybdic acid, ammonium silicon molybdate, arsenic molybdic acid, Ammonium arsenic molybdate, sodium arsenic molybdate, tungstic acid, ammonium grinder ramate, phosphotungstic acid, ammonium phosphotungstate, Silicon tungstic acid, ammonium silicon tungstate, sodium silicon grinder ramate, arsenic tungstic acid, ammonium arsenic tungstate, Sodium Arsenic Tungstate, Isopropylammonium Molybdate, Phosphorvanadium Molybdic Acid . 7. The method according to claim 3, characterized in that the reducing agent from D-glucose or from reducing Polymer compounds exists. 8. The method according to claim 1, characterized in that the layer of image-forming agent contains a binder. 809808/0756 2 7 3 ϋ υ j y 9. The method according to claim 1, characterized in that remaining as a further process step in the non-image parts imaging agent is brought into contact with an alkaline substance so that it becomes its imaging agent Loses ability. 10. The method according to claim 2, characterized in that the surface of the imaging agent is irradiated ^{with ultraviolet rays of at least 100 mJ / cm 2.} 11. The method according to claim 1, characterized in that the surface of the image-forming agent is irradiated ^{with long-wave light rays of at least 2.5 J / cm 2 after the discoloration.} 12.Imaging material, characterized by a base, an imaging layer on at least one surface of the support, the layer being an imaging agent which consists of one of the following substances: Poly acids of molybdenum and tungsten, salts or complexes of these polyacids and through a transparent polymer film on the imaging layer, at least the imaging layer or the transparent polymer film contains a reducing agent. 13. Imaging material according to claim 12, characterized in that that the image-forming material consists of at least one of the following substances: molybdic acid, sodium molybdate, Ammonium molybdate, phosphomolybdic acid, ammonium phosphorus molybdate, Silicon molybdic acid, ammonium silicon molybdate, arsenic molybdate 809808/0756 ORIGiNAL INSPECTED " ⁴ " 2736Ü38 lybdic acid, ammonium arsenic molybdate, sodium arsenic molybdate, tungstic acid, Ammonium tungstate, phosphotungstic acid, ammonium phosphotungstate, Silicon Tungstic Acid, Ammonium Silicon Tungstate, Sodium Silicon Tungstate, Arsenic Tungstic Acid, Ammonium Arsenic Wolf ramate, sodium arsenic tungstate, isoprop ^ ammonium molybdate, Phosphorus vanadium molybdic acid. 14. Imaging material according to claim 12, characterized in that that the reducing agent consists of one of the following substances: D-glucose, thiocarbamite, oxalate iron, Michlersketone, L-ascorbic acid, diphenylamine, diphenylcarbacid, titanium oxide, zinc oxide, tin oxide, lead, tin, iron, zinc, reducing Polymer compounds, each reducing polymer compound being characterized in that one of one part by weight of the compound and two parts by weight of phosphomoybdic acid and applied as a film to a polyester film and the mixture irradiated for one hour by a 250 watt mercury lamp from a distance of 20 cm shows a difference between the values of Mackbeth optical diffusion transmission density gives greater than 0.01 before and after irradiation. 15. Imaging material according to claim 14, characterized in that that the layer of image-forming material contains a weak reducing agent of D-glucose or reducing agent Contains polymer compounds. 16. Imaging material according to claim 12, characterized in that that the layer of image-forming material additionally contains a binder. 809808/0756 ~ ⁵ ~ 2733098 17. Image-forming material according to claim 16, characterized in that the binder is a polymeric compound which is soluble in water or in an alcohol, and that the
the polymeric compound forming the transparent polymer film is insoluble in water or an alcohol. 18. Imaging material according to claim 12, characterized in that that the layer of image-forming material contains a reducing polymer compound as a reducing agent and additionally contains a binding agent. 19. Imaging material according to claim 18, characterized in that the reducing polymer compound is a
contains: polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral. 20. Imaging material according to claim 12, characterized in that the forming the transparent polymer film
Polymer compound consists of one of the following substances: polyvinyl chloride, polyvinyl acetate, polyvinyllidene chloride, cellulose resins, polystyrene, polypropylene, polyvinyl carbazole, polymetacrylate resins, polyamide resins, fluororesins, rubber chloride. 21. Imaging material according to claim 12, characterized in that that the concentration of the imaging agent in the imaging layer is greater than 15% by weight. 22. Imaging material according to claim 12, characterized in that that the thickness of the imaging layer in the 809808/0756 - ₆ - ORlGfNAL INSPECTED ~ ⁶ ~ 273609B The order of magnitude is from 2 to 20 μm and that the thickness of the polymer film is on the order of 5 to 15 µm. 809808/0756