DE2425210A1 - Non-silver organic photosensitive material - with coating of hydrophilic polymer to improve keeping qualities - Google Patents

Abstract

Coating(s) (I) are used in face-to-face relation with the base (II) and non- Ag organic photosensitive compsn. (III) of a light-sensitive material. At least (I) consists of a water-soluble or otherwise hydrophilic, colloidal or synthetic film-forming polymer, esp. polyvinyl alcohol. Pref. >=1 (I) is present between (II) and (III) and (I) is ca. 1 mu thick. (II) can be a porous material (paper), a film of synthetic resin (polyester) or a glass plate, whilst (III) contains dye, dye base, dye precursor and/or polymer yielding an image when suitably exposed.

Description

Photosensitive material The present invention relates to the improvement of the storage stability properties and the improvement the densitometric, sensitometric and processing properties of organic, non-silver photosensitive films and their compositions.

It is known that photosensitive silver halide compositions generally have a good shelf life and that in contrast organic non-silver photosensitive compositions often one have poor shelf life. It is also known that the shelf life - although it can be very different depending on the specific composition - according to U.S. Patent 3,640,718 seldom more than 3 to 6 months and according to U.S. Patent 3,615,564 is usually only a few days or weeks.

The term "shelf life" generally refers to the Period in which the photosensitive properties of a photosensitive Composition - in the absence of light or other forms of influencing Radiation - do not change it or only change it to such an extent that its This does not affect usability.

However, each photosensitive composition can be used for specific purposes continue to be usable even if some of their photosensitive properties are lost change, and the term "usable shelf life" relates to that definition in a broader sense.

A limited or poor shelf life is indicated by the Change in one or more of the photosensitive properties of the photosensitive Composition.

In photographic jargon, these are light-sensitive Properties when describing the sensitometric and densitometric properties of the photosensitive composition and include but are not limited to the following: (but without ~ limitation to this) * - or shelf life 1. photosensitivity, which expresses the exposure time that is necessary to achieve a desired photographic Get result. This sensitivity can be determined by one or more empirical Formula (s) as used by Todd and Zakia (Photographic Applications in Science, Technology and Medicine, Fall 1968, p. 35), or by the energy which is necessary to obtain a certain image density, or simply through the number of stages that go through a certain stage part with a certain Exposure and light source generated are expressed.

2. Densitometric properties, usually derived from the D-Log curve E or the characteristic curve can be expressed5 which are the maximum and minimum Represents density in connection with certain exposure and processing conditions and the size of the change in density during exposure including the gamma value, the low exposure area or the "curved tail" * and the high exposure area ** describes. A poor or limited shelf life is expressed in a Change in one or more of these characteristics, such as a decrease in the maximum density or a changed gamma value or an increase in carrier plus haze that occurs during storage and not as a result of exposure and processing takes place and which is referred to as "dark fogging".

3. Processing conditions, such as development and fixing times, time intervals between the processing stages and related parameters such as temperature and relative humidity.

In case of poor or limited shelf life you can one or more of these properties change.

Although a change in the photosensitive properties listed does not necessarily have to limit the "usable storage time", in particular then not if the * ~ dead region "**" high exposure or shoulder region? 1 speed the change in the property (s) is known during the storage time, become light-sensitive Compositions preferred, their properties during prolonged storage are subject to little or no changes.

The use of hydrophilic coatings on silver halide films, Photoconductor-type imaging systems and certain photopolymerizable compositions to induce one or more advantageous properties is known and is described in numerous patents, including the following U.S. Patents: 2,732,304, 3,058,826, 3,060,026, 3,105,762, 3,279,920, 3,295 970, 3 395 112, 3442649, 3591 379 and 3700449.

It has now been found that the application of one or more hydrophilic coatings on the non-silver-containing photographic materials described below Compositions to a significant improvement in storage stability and / or one or more of the photosensitive properties of these non-silver containing properties photographic compositions leads.

In the field of non-silver-containing, organic photo-generating agents Systems are known to undergo a number of physical and chemical changes can occur which lead to poor or limited shelf life.

From G.R. image, R.C. Jones and A.E. Ames g pplied Option, 8 (12), 2389 (1969) # 7 describes that a limited shelf life for "non-conventional" Photosensitive compositions is a fundamental property that is based on the lack of a so-called "gating step" is due.

However, there remain other causes of poor or limited Shelf life and the present invention addresses these causes. Among these found causes for poor or limited shelf life belong: 1. Loss of volatile activating agent due to Sublimation; 2. Loss of other essential, highly volatile components; 3. Pollution from gaseous 4. airborne pollution natural components of the air, such as oxygen, an oxidizing agent, and carbon dioxide, that in the presence of water, another natural component of air, Forms carbonic acid; 5. Surface contact with or direct inclusion of chemical reactive or catalytic finely divided material from the air. With this finely divided Material can be a pure chemical or a mixture of chemicals or dust, which either naturally or as a result of trapped, adhering, absorbed or adsorbed chemicals, either in solid, gaseous or liquid form, is reactive.

It has now been found that the shelf life of non-silver containing, organic photosensitive films are extended or otherwise improved can be achieved by applying one or more polymer coatings to these films, at least one of the coatings being a non-dissolving, water-soluble one or otherwise hydrophilic, colloidal or synthetic, film-forming Polymer is. It has also been found that such a coating is a or more of the photographic properties of the film identified in the foregoing have been described in connection with the light-sensitive properties, can improve or change advantageously.

It is also generally believed that most if nor does it necessarily apply to all of the photosensitive compositions described herein Reactions based on free radicals take place through exposure can be caused by radiation with interaction. Many kinds of chemical Reactions, especially reactions based on free radicals, above all Chain reactions, based on free radicals, can be caused by many different other chemicals, including those mentioned above as causes of bad Storage stability have been described. An investigation the auto-oxidation mechanism shows that the oxygen is based on reactions of free radicals due to its chemical behavior and its ubiquitous Nature is of particular importance. With many, if not all, of this one the photosensitive compositions described, chemical reactions take place, those as either oxidation-reduction type or acid-base type reactions or in some cases can be classified into both types. So it is possible that deliberate acid contamination of the photosensitive composition and / or bases and / or oxidizing agents and / or reducing agents - depending on the type the special photosensitive composition - the nature of the image-forming reactions affects, in addition to and / or independently of the effects that the impurity has an impact on the shelf life of the composition.

It goes without saying, of course, that the causes found so far for poor shelf life is not necessarily the only cause and that they are not necessarily in the case of special film compositions the cause of a limited shelf life or altered photographic Must be properties. Also, the coating does not necessarily have to be only in this one act as a lock or as a lock at all.

The object of the present invention is to improve or lengthen it the shelf life of organic, non-silver-containing, light-sensitive, image forming systems.

A further object according to the invention is to improve or advantageous Change in one or more of the photosensitive properties of these photosensitive systems, as well as improving or beneficial modification on one or more of the processing properties of the photosensitive systems.

Another object of the present invention is to improve the optical development process disclosed in U.S. Patent Nos. 3,510 300 and 3,618,504, as well as an improvement in abrasion resistance the photosensitive layer against mechanical abrasion.

The following are preferred embodiments of the present Invention described: Light-sensitive compositions In the case of light-sensitive * compositions, their storage stability and / or photographic properties are improved according to the invention are to be, it is generally such compositions in which one of the following changes takes place for the purpose of image generation, The purpose of identifying the general type of composition is: * under. "photosensitive" what is meant here is the response to any kind of usable rays.

1. Formation of a dye image from colorless precursors and / or on a colorless background and / or formation of a dye image from one different colored precursor dye; 2. Disappearance of color from one colored background, commonly referred to as a decolorization or fading process *; 3. Certain photopolymerizable compositions - regardless of whether there are color changes associated with it - create an image as a result of a change in optical Properties and / or the solubility properties.

These compositions comprise as an essential image-forming element at least one organic or organic dye precursor and / or at least an organic or organometallic dye or at least one polymerizable Component or crosslinkable polymeric component produced by the action of suitable radiation, such as visible light, ultraviolet or infrared rays, X-rays, gamma rays or electrons, at least one of the listed Causes change.

These compositions generally comprise a sensitizer, to make the composition sensitive or more sensitive to exposure to radiation close. The compositions can also contain an additional ingredient, such as a spectral sensitizer, sensitivity enhancer, agent for enhancing image density and stabilizing agents for improved processing, to prevent "dark haze" and to extend shelf life as well as other additives for specific purposes.

* "dye-bleach or bleachout process" The first general Kinds of photosensitive compositions to which the present invention can be used, contains as image-forming elements one or more dye-producing (s) Asinte) or furfurlid (e), styryl, cy <m or merocyanine dye bases, leuco compounds, which generally have a central carbon atom on which 2 or 3 aryl groups are bound, as in the di- or triarylmethane derivatives, or the part of a represent heterocyclic ring in connection with condensed rings> like the xanthenes, tnioxanthenes, acridines, anthracenes, and the like. To the leuco compounds include the alkyl, allyl and aryl ethers and carbinols of these compounds and the leuco dye bases. They also include the aryldiazonium compounds that are able to produce a dye when combined with another compound, which is generally referred to as a color coupler and which is general is an arylamine or a phenol is coupled. Compositions of these the first type are detailed in the U.S. patents listed in Tables 1, 2, 3 and 4 described ur.-t are also described in some of the following examples.

Table 1 Image dye-forming aryl and heterocyclic amine systems U.S. Patent Nos .: 3,042,515 3,394,391 3,413 121 3,615,477 3,042,516 3,394 392 3 450 532 3 615 564 3 042 517 3 394 393 3 490 907 3 617 288 3 102 029 3 394 394 3 539 346 3 634 085 3 147 117 3 394 395 3 554 754 3 637 390 3 164 467 3 410 687 3 582 342 3 649 284 3 598 583 Table 2 Various image dye-forming agents Systems: phenols, organometallic systems, pyrans, etc.

3,446,621 3,554,754 3,490,907 3,642,479 3,647,448 Table 3 Image Dye Forming Finishes Dye bases.

A. Styryl, cyan, merocyan, and vinylidene dye bases.

3 095 303 3 109 736 3 533 792 3 578 455 3 10Q 703 3 112 200 3 554 753 3 578 456 3 102 Q27 3 121 633 3 558 317 3 582 332 3 104 973 3 342 603 3 563 749 3,624 228 3 106 466 3 510 304 3 573 046 3 640 718 3 576 799 3 642 479 3. Leukocarbinols and -ether, Schiff bases, color indicators.

3 102 029 3 112 200 3 481 739 3 578 455 3 102 810 3 443 945 3 486 898 3 597 211 3 573 Q46 3 660 096 Table 4 Image Dye Forming Finishes Leuco dyes.

3,042,515. 3,351,467 3,486, .398 3,578,1155 3,102,810 3,377,167 3.1189, xjó8 3,579,336 3,113,024 3,390,994 3,493a376 3,579,337 .3,121,632 3,390,995 3,510,309 3,579s342 3,121,633 3,390,996 3,522,044 3,598,592 3,140,948 3,390,997 3,525,616 3,615,565 3,140,949 3,395,018 3,527,517 3,615,566 3,272,635 3,418,118 3,527,640 3,6211,228 3,281,242 3,445,232 1 3,537,856 3,647,467 3,2840205 3,445,233 3,552,973 3,652,275 3,285,744 3,445,234 3,560,211 3,658,542 3,342,595 3,449,379 3,563,750 3,658,543 3,342,602 3,481,739 3,563,751 3,660,096 3,342,604 3,484,238 3,573,046 3,666,466 ~ 3,573,911 3,697,280 To the second general type of photosensitive Compositions to which the present invention can be applied include Compositions containing one or more styryl, cyano, or merocyanine dyes; Di- or triarylmethane dyes and their heterocyclic derivatives with condensed Contains rings, including photo reducible species such as methylene blue. Compositions of this general type are found in the U.S. patents listed in Table 5 described.

Table 5 Discoloration Image Forming Systems.

3,102,027 3,155,509 3,104,973 3.1118,118 3,112,200 3,443,545 3.1514,416 3,495,987 3,515,552 A third general type of photosensitive composition, to which the present invention can be applied are compositions which contain N-vinylamines. Examples are the compositions that in the U.S. patents listed in Table 6.

Table 6 Image-forming N-vinylamines.

3,042,517 3,202,507 3,443,945 3,527,639 3,042,518 3,275,443 3,450,532 3,554,752 3,046,125 3,330,659 3,512,975 3,573,911 3,056,673 3,359,105 3,522,044 3,620,733 3,147,117 3,374,094 3,525,616 3,653,886 3,697,276 The photosensitive Composition belonging to one or more of the above types becomes dissolved in or mixed with a suitable binder or solvent (s) and applied to a paper or a transparent film base, namely-after one of the many known coating processes, e.g. spin coating Draw bar and dip coating or the photosensitive composition may optionally be dissolved in a suitable solvent or solvents are dissolved or mixed with them without a binder is used, and then an absorbent paper backing can be impregnated therewith will.

To the disclosures of those listed in Tables 1, 2, 3, 4, 5 and 6 Patent specifications are expressly referred to here, as is all of them named therein Compositions, and not just the main image-forming ingredients, but also the activating, additives, sensitizing and binding agents and other ingredients that can optionally be added.

coating To the hydrophilic colloids suitable according to the invention or Synthetic polymers include those listed in Table 7 and the like Materials.

The intended coating is in a suitable solvent or Solvents and after one of the many known coating processes, such as drawing, pouring, dipping, rotating or meniscus coating on the photosensitive Layer applied. Depending on the specific photosensitive composition, a specific solvent or mixture of solvents is preferred will. For example, to improve the adhesion of the coating to the photosensitive To improve the layer, a solvent would be suitable, which also contains the binder the photosensitive layer is sufficiently soluble that the surface softens on contact with the coating solution, but is not so highly soluble, that # the surface is greatly changed.

In order to obtain a lower adhesion to the mechanical removal To facilitate the coating, a solvent would be suitable in which the binder the photosensitive layer is insoluble or less soluble.

With certain photosensitive compositions, a certain amount may be desirable chemical interaction with some solvents necessary for the hydrophilic coating might be considered to occur. The solvent (s) should so. be selected to avoid such interaction.

Another way to avoid these unwanted interactions and likewise undesirable interactions between the photosensitive layer and Eliminating the coating itself consists in adding one or more intermediate coating layers to be applied between the photosensitive layer and the coating Coating means the outermost coating layer. The intermediate shifts don't have to be It must also be hydrophilic, but any suitable hydrophobic one Act polymer, such as polystyrenes, Pclymethacrylate, polycarbonates, Pol-yphenylenoxde, Copolymers of styrene and methacrylates, copolymers of styrene and Butadiene, all commonly used as a binder for photosensitive compositions can be used in accordance with the present invention. If these intermediate layers are selected accordingly, they form a barrier against the undesired interactions, those between certain photosensitive compositions and certain hydrophilic ones Coating and / or coating solvents can take place. A corresponding Selection of the intermediate layers also allows for a more gradual change in the chemical nature and the solubility properties of the photosensitive high layer up to the coating, which in turn gives a greater choice in the use of the coatings and the solvent while avoiding undesirable interactions with the photosensitive layer permitted.

To optimally improve the shelf life and / or other Photosensitivity properties of certain photosensitive compositions To achieve this, certain coating materials may be preferred. If the main task of Coating consists in the loss of the volatile activating agent or other volatile components present in the photosensitive layer are to be prevented, any hydrophilic material and even that is suitable hydrophobic materials that are not compatible with the volatile component (s) are penetrable. In such photosensitive compositions where it appears necessary to keep away oxygen or the presence of oxygen To keep it to a minimum, a coating that is opaque to oxygen is preferred has a low permeability. For this purpose, polyvinyl alcohol is used as a coating material preferred.

Polyvinyl alcohol is also preferred as a coating in cases where the photosensitive compositions against gaseous, atmospheric pollutants, such as sulfur dioxide, nitrogen oxides, halogens and halogen acids, are sensitive, since it has only a low permeability for such gases.

The thickness of the coating or coatings depends on the particular special function and the special photosensitive composition. if The main or sole function is to prevent the escape of a volatile hydrophobic component, such as one of the common activating agents, e.g. iodoform or carbon tetrabromide, only a very thin coating is needed.

In these cases the coating can be thinner than 1 micron.

When impermeability to gases such as oxygen is desired thicker coatings of at least a few ~ oil "(= 0.025 mm) are preferred Use of thicker coatings is possible and is only supported by considerations regarding the optical clarity and mechanical limitations of the total thickness of the complete light-sensitive material.

Instead of applying the coating in a solvent the coating also as a dry film in the form of a laminate, if appropriate in conjunction with an adhesive. In some cases where the Compatibility between the photosensitive layer and the coating is sufficient is good, one can achieve satisfactory adhesion when pressure is applied to the Laminate is exercised. In other cases an adhesive can be used, preferably a pressure sensitive adhesive that allows removal of the coating made possible without destroying the underlying photosensitive layer.

The following examples serve to explain the type of present invention and the improvement of storage stability and other photosensitive Properties.

The photosensitive compositions shown in Tables 1 to 6 are prepared by dissolving the ingredients in a suitable solvent-binder solution Solution brought together in the darkroom or in complete darkness the individual components I get used to in the examples of the mentioned patents listed order in the solvent-binder solution and then mixed to dissolve before the next ingredient is admitted. After the composition has been thoroughly mixed, will applied them to a suitable substrate. Suitable substrates are, for example Polyester or other synthetic polymers, glass or paper that are compatible with the in Table 7 mentioned hydrophilic polymers is impregnated accordingly, or all other suitable substrates, provided they have a low permeability to it Own gas.

When the photosensitive layer is applied to the selected substrate a second layer is applied to the photosensitive layer. This second layer or "coating" 1 consists of one selected from Table 7 suitable hydrophilic binder or resin.

Table 7 Coating materials.

Gelatin Dextrin Casein Folysaccharide Starch Acetate Carboxymethyl Cellulose Starch hydroxyethyl ether Hydroxyäthylzellulo se long chain alkyl starches guar gum Carboxymethyl cellulose Gum acacia Alkyl hydroxyalkyl cellulose Colloidal albumin Polyvinyl alcohol polyvinyl methyl ether polyvinyl pyrrolidone polyacrylic acid and salts Agar-agar Polyacrylamides Gum arabic Ethylene oxide polymers Dextran The complete photographic material consisting of substrate, photosensitive layer and coating or coatings, can be exposed and processed in a wide variety of ways, which depends on the purpose of use of the photosensitive system. If it is for example a photosensitive composition suitable for duplication through direct contact ("roll-to-roll duplicationn"), i.e. through the so-called contact process, is provided, the coating or the hydrophilic layer can either be from the surface the photosensitive layer must be removed before this with the to be reproduced Original negative or positive is brought into contact; or - if the coating is thin enough not to affect the resolution transfer properties of the photosensitive Affecting layer - it can be left on and in a later one Stage of the machining cycle with a suitable solvent stripped or removed. It has been found that in the case of ~ direct recording materials "* it is not necessary to remove the coating immediately before exposure, since With this process there is no direct physical contact with an original negative or -positizSfilms as is necessary with the contact method, but the image generation is made by means of an optical system. In those systems where developing is necessary, i.e. where a latent image is directly recorded or is recorded, which is then later to become a visible image, the In some cases it may be necessary to remove the coating prior to development the parameters for developing and / or the associated photosensitometric Properties are changed as a result of the coating, it is preferred in some cases to remove the coating prior to developing, while it is preferred in other cases is to leave the coating intact until after development, whatever of the respective special photosensitive composition and / or from the desired photographic Results and / or processing conditions.

For example, if a photosensitive system that has a coating is exposed to a latent image exposure and the development of this latent image is delayed beyond the shelf life of the uncoated material leave the coating intact and the latent image can become one to be developed later. However, if the material is on the fly, as in the contact process, the coating can be used immediately after the Exposure to be removed before fusing. It has been found to be beneficial is to strip the coating prior to the fusing step either by stripping or by a suitable one Remove solvent. Fixing the exposed, * ~ direct acquisition material" but undeveloped product, i.e. a contact process Copying material can be made by heating the product to a certain temperature can be achieved, whereby the volatile activating agent is removed. at Other systems can fix it by washing the product in a suitable one Solvents are made, the activating agent components being selective extracted. In those cases where the photosensitive composition is without Solvent or can be fixed without volatilization of the activating agent, for example, those compositions according to U.S. Patent Nos. 3 390 994, 3 390 995, 3 390 996 and 3 445 233, which can be fixed by light, the coating does not need to be removed.

Example 1 A photosensitive composition was prepared by dissolving the following ingredients in 12 ml of 1,2-dichloroethane: 1.0 ml a solution obtained by dissolving 600 mg of polyphenylene oxide in 3.5 ml of tetrachloroethane had been prepared, 450 mg of 1,1-bis (p-dimethylaminophenyl) ethylene 250 mg of iodoform 35 mg 2,6-di- (tert-butyl) -cresol 10 mg triphenystiben 16 mg 4-picoline-N-oxide with red darkroom lighting, the composition was about 0.04 mm (wet thickness) applied to polyethylene terephthalate "500D Mylar", several Air-dried minutes and then at 360 nm through a Kodak step wedge 1A exposed. Then the film was fixed by heating to about 71 ° C. for 2 minutes. Exposure to 360 millijoules gave a maximum density (Dmax) of 1.40, a carrier plus fog density (tT + S) of 0.04 and a photosensitivity of 150 (required millijoules to produce a net density of i, o).

The same photosensitive composition was made with a 4.5% strength Solution of polyvinylpyrrolidone yellowed in water (NaB thickness 0.15 mm), Allowed to dry for 10 minutes and then done in the same way as the uncoated Film exposed. Then the coating was gently agitated in a water bath removed, the film was air dried and then at 71 ° C. for 2 minutes fixed. The essex score, vehicle plus fog score, and photosensitivity were the same exactly those of the uncoated film.

Another photosensitive film of the same composition was coated with PVP and then exposed and exposed for one minute Heat fixed to 710C without removing the coating first. After that, the The coating was removed by washing, the film was air-dried and then Fixed at 71 ° C for 2 minutes. The same exposure resulted in 360 millijoules to a Dmax value of 2.46, a T + S value of 0.04 and a photosensitivity of 10.

Another film was coated (0.15 mm wet thickness) from a 5% solution of hydroxypropyl cellulose (Hercules Klucel EF) in propanol, and allowed to air dry for 30 minutes. The film was rated 360 millijoules exposed, then fixed for 2 minutes at 710C without prior removal of the coating. A photosensitivity of 78, a Dmax value of 1.70 and a were obtained T + S value of 0.04.

Example 2 In the dark, a photosensitive composition was prepared prepared by adding the following ingredients in 4.0 ml of a proprietary solution of polyvinyl chloride The following were dissolved in tetrahydrofuran: 150 mg of 3-ethyl-5 - [(3-ethyl-2- (3H) -benzothizolylidene) -ethylidene (2-quinolylmethylene) -4-thiazolidone 150 mg 2-mercaptobenzothiazole 800 mg carbon tetrabromide 3.0 ml of methylene chloride. The solution was applied to a polyethylene terephthalate support "500D Mylar" applied (NaBdicke 0.04 mm), with a drawing applicator ("draw bar applicator ") was used.

After 30 minutes, the dried film was checked with a high pressure mercury arc sensitometer illuminated with 5 wattsec / cm2. DanrX was the film through two consecutive Washes with a toluene-acetone mixture (4: 1) fixed, whereby unreacted Starting materials have been removed from the film, thereby allowing an examination of the image and density measurement with normal room lighting were possible. One received a Laughing blue-black image with a density of 2.5 at a T + S value of 0.08, which is measured with the aid of a UV densitometer using integrated Light from 3660 - 4358 i was detected. After a storage period of 4 months at room temperature ~ (about 24 ° C.) was obtained with the same exposure and processing of an originally identical film a blue-black image with a density of only 1.5 with a T + S value of 0.02.

Another film of the same composition was released after seeing 3Q Had been air-dried for minutes with a 5% aqueous solution coated in gelatin (photographic quality), then in a refrigerator for 5 minutes wedged for a long time, then dried with a gentle stream of warm air for 10-15 minutes and then stored at room temperature for 4 months. After that the movie was but was exposed and fixed in the same manner as the uncoated film the coating is removed by washing with water before fixing. One received a bluish black image with a density of 2.5 and a carrier plus fog value of 0.08, which corresponds to the values obtained by exposing the fresh film received.

Another film made in the same way and 39 minutes which had been air dried was spin coated with a 5 'own aqueous solution of polyvinylpyrrolidone coated. After the plating After air drying for 15 minutes, its thickness was determined with a permascope was measured and found to be less than 1 micron. After this the film for 4 months stored at room temperature (approx. 24 ° C) it was exposed and processed in the same way as that in this one Example described film coated with gelatin.

A blue-black image with a density of 2.4 and one was obtained Carrier plus haze value of 0.05.

Example 3 In the dark, a photosensitive composition was prepared produced by leuco malachite green (100 mg), 4-picoline-N-oxide (15 mg> and Carbon tetrabromide (1.4 g) in 4.0 ml of a 15% solution of Pliolit 58A in benzene have been resolved. This solution was in a wet thickness of 0.04 mm on a polyethylene Enterephthalate carrier ~ 300D Mylar't using a draw applicator applied. After the film has been air dried for several minutes it was exposed to 10 milliwatt seconds at 380 nm.

The film was then fixed by being in a solution of petroleum ether / acetone / Stoddard solvent (8: 2: 1 = volume) was washed. A lightfast green image was obtained with a density of 1.50 and a carrier plus fog value of 0.05, where a Wratten filter 72B was used. After a storage period of 3 hours, it was turned off Film of the same composition exposed and processed in the same way a green image with a density of only 0.45 and a carrier plus fog value from 0.07 to.

Another film made from the same composition and dried for several minutes, was treated with a 15% aqueous Solution of polyvinyl alcohol using a draw applicator in a Wet thickness of 0.08 mm coated. After the film air dried for 15 minutes it was stored in the dark for 7 days and then just like the uncoated film exposed at 10 milliwatt seconds. The exposed film was agitated in water for a few minutes at room temperature to cover the coating remove, then air dry for several minutes and then in the same way like the uncoated film, fixed by washing in a solvent. That The green image obtained had a density of 1.45 and a carrier plus fog value of 0.06, which was determined using a Wratten 72B filter.

EXAMPLE 4 A photosensitive composition was prepared by adding leuco crystal violet (100 mg), 4-picoline-N-oxide (20 mg), 2- (p-dimethylaminostyryl) -quinoline (64 mg) and carbon tetrabromide (1.4 g) in 4.5 ml of a proprietary solution of polystyrene were dissolved in benzene. As in Example 3, using a puller a film is produced which is exposed to white light of 58,000 mos and then fixed became. A rodent image with a density of 1.86 and a carrier plus fog value was obtained of 0.07 as found with a Wratten 94 filter.

The same exposure and processing of a film of the same composition, which had been stored for 5 hours gave an image with a density of 0.80 and a carrier plus fog value of 0.07.

Another film of the same composition was made, that, after being dried for several minutes, with a 10% solution of Polyvinyl alcohol was coated using a spin coater.

After air drying for 15 minutes, it became he exposed with 35,000 mos, whereby you get an image with a density of 1.85 and a Carrier-plus-fog score of 0.06 was obtained, which is essentially the same as the fresh prepared film.

Example 5 A photosensitive composition was prepared by 2,7-bis (dimethylamino) -10-p-dimethylamino-phenyl-9, 10-dihydro-9, 9-dimethylanthracene (100 mg), 4-picoline-N-oxide (20 mg), 4 - (- p-Dimethylaminostyryl-quinoline (64 mg) and carbon tetrabromide (1.2 g) in 4.5 ml of a 10% solution of polystyrene were dissolved in benzene in the dark. In the manner described in Example 3 was made a film.

After drying it for several minutes, it became with white. # Light of 20 mos exposed, after which an exposure over the whole area with red light using a Wratten 893 filter. The movie that was fixed by washing with a solvent as in Example 3, instructed purple image with a density of 2.2 and a carrier plus fog value of 0.20, which was determined by a Wratten filter 94. After one hour of storage obtained with a film made from the same composition with the same Exposure and processing an image with a density of 0.90 and a carrier plus fog value from 0.3.

Another film made from the same composition was with a 10% solution of polyvinyl alcohol dissolved in ethanol, coated (thickness 0.08 mm.

After air drying for 15 minutes, it became he exposed to white light of 20 mos in the same way as before and the The coating is then removed with water.

After the film was air dried, it was placed in the developed and fixed in the same way as the uncoated film. One received a density of 2.5 and a carrier plus haze value of 0.25. Having a similar coated film had been stored for 1 hour, identical ones were obtained Exposure and processing conditions an image with a density of 2.4 and a Carrier plus haze value of 0.24.

EXAMPLE 6 The photosensitive film of Example 5 was coated adding a 0.04 mm thick sheet of polyvinyl alcohol using pressure rollers Room temperature was applied to the film.

After the film was stored for 1 day, it became the same Way exposed, and then the coating was removed using a strip of masking tape attached to it and the coating slowly peeled off. The picture had a density of 1.5 and a carrier plus haze value of 0.17.

Example 7 The coated photosensitive film of Example 6 was made exposed after 5 days of storage as in Example 5 and then developed, the Coating has been left thereon. The coating was then removed by peeling it off and the film fixed as in Example 5. An image was obtained with a density of 1.9 and a carrier plus haze value of Q, 21.

Another film was edited in the same way, with the However, the coating was only removed after 30 minutes.

An image with a density of 2.2 and a carrier plus was obtained -Veil value of 0.25.

Example 8 The photosensitive film according to Example 5 was coated by using a sheet of polyvinyl alcohol 0.075 mm thick a pressure sensitive adhesive ~ Scotch y906411 was applied to the film. After 3 days of storage, the film was exposed and processed as in Example 7. An image with a density of 2.2 and a carrier plus fog value was obtained of 0.24.

EXAMPLE 9 A photosensitive solution was prepared by using 600 mg of diphenylamine and 700 mg of carbon tetrabromide in 4.5 ml of a solution of the above Polystyrene were dissolved in benzene. This solution was in a NaBdicke of 0.04 mm applied to a film carrier by means of a draw applicator.

After the film was air dried, it was 8 minutes long exposed through a step wedge with a sun lamp 'GEt'. The exposed The film was then heated to 1000 ° C. for 3 minutes. A blue image was obtained with a maximum density of 2.4, which was determined with the aid of a Wratten filter 94 became. After storage in the dark for 6 weeks, this film was obtained at same exposure and processing an image with a maximum density of only 0.95.

A film of the same composition was rolled under Print with a covering film made of polyvinyl alcohol with a thickness of 0.85 mm. After six weeks of storage in the dark, the coating was peeled off and the film is exposed and fixed in the manner previously described.

The same blue image was obtained with a maximum density of 2.3.

Example 10 A photosensitive film was prepared according to Example 9, however, 700 mg of 3-methylindole in the solution instead of the 600 mg of diphenylamine were used. The film was exposed and fixed in the same way, and a black image with a maximum density of 1.90 was obtained. After a Storage of 3 weeks at room temperature in the dark was obtained with the film, which had no coating had a maximum image density of only 0.55.

A newly prepared film of the same composition was made with a 5, 'own aqueous solution of gelatin (photographic quality) in a wet thickness coated by 0.08 mm, then refrigerated for 5 minutes and then for 6 weeks stored in the dark and at room temperature. After the gelatin has been removed was obtained when the film was exposed and processed in the above-described manner Way an image with a maximum density of 1.20.

EXAMPLE 11 A photosensitive composition comprising 1 g of polystyrene, 1 g of N-vinyl carbazole and 200 mg of pentabromoethane dissolved in 10 ml of benzene were, and the 0.4 g of tin (II) iodide contained, as a 10-violin solution in a Mixture of benzene and ethylene dichloride in a ratio of 1: 1 has been added, was in a wet thickness of 0.08 mm on a polyethylene terephthalate carrier "500D Molar "and allowed to air dry for 5 minutes Exposure to a sun lamp "GEn" for 10 minutes and heating to 1100C a brown-black image was obtained for 2 minutes.

After watching the film for 1 week in the dark at room temperature stored, a noticeably lighter brown color was obtained with the same treatment Image.

A film of the same composition was coated with polyvinyl alcohol, in the form of a 5% aqueous solution with the help of a pulling device in a Wet thickness of 0.08 mm was applied. After storage for 3 weeks in the dark a deep brown-black image was obtained with the same treatment (with the PVA between removed after exposure and fusing).

Example 12 A photosensitive composition containing iodoform (200 mg), 2,4-diamino-1-chlorobenzene (150 mg), m-phenylene (30 mg), difurfurylidene pentaerytheritol (100 mg) and polystyrene (100 mg) dissolved in 4 ml of chloroform; was in a Wet thickness of 0.04 mm on a polyester carrier "500D Mylar" and applied to the Air dried. Then she was dated for 30 seconds with a special lamp Type "Sylvania Sun Guntl (625 watts) exposed from a distance of 38 cm and then exposed heated to 1490C. A brown-black image was obtained. After the film 3 weeks long stored in the dark at room temperature was obtained from the same Exposing an image with a much weaker tint.

A film prepared in the same way was in a wet thickness of 0.08 mm coated with a 10% aqueous solution of polyvinyl alcohol, and one let it air dry for 30 minutes. Then the movie was in the same Way as the uncoated film exposed, and the coating was through faint Moving away in a water bath. After drying, the film was modified to 14906 heated, and the same brown-black image was obtained. After 6 weeks of storage in the dark, an identical brown-black color was obtained with the same exposure and processing Image.

Example 13 A positive working photosensitive co-operation was established Settlement prepared by adding 8 g of carbon tetrabromide with a solution of 0.2 mg 5- methyl-4- (1) -ehinolylidene) -äthyliden7-2-t (r (1-methyl-4 (1) -quinolylidene) -methy17-4- (5) thiazolone ether p-toluenesulfonate in 30 ml of acetone, 30 ml of dimethylformamide and 30 ml of methanol were mixed, this composition was applied to paper, whereby a sheet colored blue was obtained. Immediately after drying, the sheet became in a wet thickness of 0.15 mm with a 15% solution of polystyrene dissolved in Benzene, coated and then air dried for 5 minutes. After that it was the sheet coated in the same way on the second side. Then it was exposed through a suitable negative with a photo lamp, and one obtained a direct, positive, high-contrast copy in which the discolored areas were white.

The copy was made by heating at 1100C for 10 minutes in one Fixed air oven. A similar film was produced after 1 week of storage exposed in the same way. Only a barely perceptible discoloration took place.

Another, freshly made, coated with polystyrene The sheet was made of a 10-ply aqueous polyvinyl alcohol solution at a wet thickness of 0.15 mm applied on both sides.

After the film was stored for 2 weeks at room temperature in the dark was obtained, one obtained with the same exposure with a photo light emitter similar direct positive high-contrast print. The polyvinyl alcohol coating was carefully removed with masking tape and the print then fixed at 1100C.

Example 14 To 675 ml of a solution of acetone and N, N-dimethylformamide with a volume ratio of 50:50, 0.5 ml of a 0.1 ml solution of tris (4-diethyiaminophenyl) methane were added in acetone, 1.5 ml of a 0.1 molar solution of trifluoroacetic acid in acetone, 0.5 g of polyethylene glycol (Molecular weight 200) 0.25 ml of a 0.1 M solution of 1,4-naphthalenediazonium oxide in acetone / N, N-dimethylformamide (see above: see above) and 0.5 ml of a 0.05 M solution of CBr4 given in acetone. The solution was applied to paper and then in air dried. The paper was then covered with polystyrene on both sides as in example 13 coated. Followed by imagewise exposure through a Corning 7-54 "filter exposure through a "Corning 0-51," filter gave a stable one purple image. With a similar exposure after several weeks of storage of the paper, only a faint purple image was obtained.

Another impregnated photo paper coated with polystyrene was coated on both sides with polyvinyl alcohol as in Example 13. To After a few weeks of storage, a purple color was still obtained with the same exposure Image whose intensity is comparable to that of the image obtained on fresh paper was.

Claims (8)

P a t e n t a n 5 n u c h-e: 1. Photosensitive material, characterized in that it -im essentially consists of: a relatively thin carrier layer; one that does not contain silver organic photosensitive composition applied to this support layer is; and at least one coating overlying the support layer wld the photosensitive Layer * has been applied. 2. Material according to claim 1, characterized in that the carrier an absorbing material X preferably paper and that the light-sensitive Composition is present in the pores of this absorbent material and from this is worn. 3. Material according to claim 1, characterized in that the carrier layer a film made of synthetic resin, preferably a polyester., or a glass plate is. 4. Material according to claim 1-3, characterized in that the coating a hydrophilic material, preferably polyvinyl alcohol. 5. Material according to claim 1-4, characterized in that it is as image-forming component at least one dye, a dye base, a Contains dye precursors and / or a polymeric component that when exposed generate an image of a suitable radiation * ~ face to face relation " 6th Material according to claims 1-5, characterized in that there are several coating layers has at least one of which is made of a hydrophilic material. 7. Material according to claim 1-6, characterized in that at least a coating layer between the support layer and the photosensitive layer is present. 8. Material according to claim 1-7, characterized in that the coating about 1 micron thick.