DE2052648C2 - Photographic recording material - Google Patents

Description

The invention relates to a photographic recording material operating according to the silver salt process, which in the form of a permanently maintained laminate on a layer support is a photosensitive Has emulsion layer, which silver halide solid solution and silver precipitation nuclei in such a concentration that in the emulsion layer when developed in the presence of a silver halide solvent a positive silver image emanating from the unexposed silver halide solid solution high opacity, the optical density of which is inversely proportional to the imagewise exposure of the Is emulsion. A recording material of this type is the subject of the older DE-OS 20 36 213.

In general, the silver salt process, mostly in the form of a silver salt diffusion transfer process, allows the creation of a positive SiI-ber (transfer) image by essentially simultaneously with the development of a recording exposure of a photosensitive silver halide emulsion generated latent image by the accompanying reaction of an additional silver halide solvent with relatively unexposed and undeveloped silver halide of the emulsion an imagewise one Distribution of a soluble silver complex salt generated as a function of the exposure exposure. This image-wise distribution of a soluble silver complex salt thus obtained becomes at least partially transferred in the direction of a suitable image receiving element and in this by precipitation of the silver creates the desired positive silver image from the silver complex salt.

It is already known in this context, see Edwin H. Land, One-Step Photography, Photographic Journal, Sect. A, pp. 7-15, Jan. 1950 that by suitable formation of the silver receiving layer as an unusually effective silver precipitation environment for the silver precipitated in the silver receiving layer exceptionally high opacity, d. H. Opacity related to the amount of reduced silver compared to that negative silver generated by development in the silver halide emulsion can be obtained. To create In this effective silver precipitation environment, precipitation nuclei or nuclei can occur in the silver receiving layer arranged in clusters, the diameter of which is directly proportional to the mass of the in the Image receiving layer is image silver deposited by in situ reduction. Through this training lets achieve that the precipitation of the image silver in association with the clusters of silver precipitates with the in The required density is directly related to the physical parameters of these clusters of germs and size is done. In this way in situ

Precipitated image silver enables positive imaging in which the elemental silver in the Image receiving element can have an extremely high opacity, for example on the order of magnitude from 5 to 15 times, or more, the opacity of the elementary silver of the negative silver image in the Silver halide emulsion layer can be.

From US Pat. No. 2,861,885, there is already a method based on the silver salt diffusion transfer process working so-called integral recording material for generating so-called composite images known, d. H. a recording material in which both a negative and a positive image are superimposed can be generated with each other and viewed without separation. Here, the photosensitive silver halide emulsion with full development of their exposed areas depending on negative silver image produced by the exposure exposure has a relatively low maximum density, im Compared to that in the adjacent image receiving layer due to a highly effective silver precipitation environment of the type mentioned above produced positive silver image of high maximum density. According to the information in the US patent 28 61885 can determine the opacity of a given amount in the composite image obtained afterwards Image silver in the image receiving part 14 to 15 times higher than the opacity of an equal amount of image silver in the silver halide element, so that for slide purposes, d. H. for viewing the composite image in transmitted light, a maximum negative density of Up to 1.0 density units can be permitted if the maximum positive density is 4 times as large or greater. Hence, this is a composite image recording material obtained unseparated after developing treatment and positive image formation after the silver salt diffusion transfer process known, which is based on the knowledge that by certain conditions (Creation of a strong silver precipitating environment) the positive image as part of the silver salt diffusion transfer process can be produced with a significantly higher opacity than the negative image, so that both images are essentially free of interference can be viewed, both in reflection and when viewed as a slide im translucent light.

The subject of the earlier mentioned DE-OS 20 36 213, of which the present invention goes out, on the other hand, is also an integral recording material in which negative and Positive image can be generated in one and the same layer, namely in the emulsion layer itself, other than the light-sensitive silver halide (mixed) crystals also contain silver precipitation nuclei. This is it thus a recording material for producing a direct positive silver image, although after the Silver salt process works, but strictly speaking it is not a diffusion transfer process because the positive image as I said, produced by in-situ precipitation of the silver complex salt in the negative layer itself will. Such a recording material results in a surprisingly high sharpness of the positive image through the Elimination of a significant lateral diffusion, and is therefore particularly suitable for training as after the Color photographic recording material operating on the principles of additive color photography through integration an additive color grid layer in permanent connection with the recording material through which the exposure and the later viewing of the composite image take place, due to the high sharpness of the positive image generation due to the lack of significant diffusion also slight Misalignments between the color raster and the positive image can be avoided.

The recording material according to the older DE-OS 20 36 213 contains a special emulsion layer, which contains silver precipitation nuclei dispersed in an effective concentration, which after the

ίο Taking exposure and developing treatment with one a silver halide developer and a silver halide solvent treatment liquid containing one of the unexposed silver halide crystals The derived positive silver image results in a higher opacity than that of the exposed ones Has a negative silver image derived from silver halide crystals

Specifically, the light-sensitive silver halide emulsion in the recording material according to FIG the older DE-OS 20 36 213 due to their special training depending on the exposure an elemental silver image when developed in the presence of a silver halide solvent of a previously unknown character. As explained in detail in the older DE-OS 20 36 213 is the image silver that results from the direct development of exposed silver halide crystals in an emulsion of the specified type, d. H. of exposed silver halide crystals, those directly immediately in the same An effective concentration of silver precipitate is assigned, in the presence of a layer Silver halide solvent, due to the practically complete absence of a "fiber" - or "thread" - Structure marked. The image silver structure obtained in this way is essentially elementary Silver grains or silver particles with a diameter substantially the same as the original diameter of the emulsion forming unexposed photosensitive crystals of the same diameter. It has Surprisingly show that on development of the exposed silver halide crystals of the emulsion in immediate vicinity with silver precipitate nuclei present in an effective inhibiting concentration reinforcement with a treatment liquid containing a silver halide solvent the optical density of the negative silver image obtained beyond the value as determined by elementary Silver parts or grains are given, the diameter of which is directly related to the original Crystal diameters in the emulsion is given and in general according to the prior art in the field of high sensitivity photographic materials, a value in the range of about 1 to 3.5 microns can be effectively avoided. Such an enhancement of the optical density of the The initial silver image can otherwise be caused by an increase in the image grain diameter Growth occurs on the crystal surface, either directly or through the formation of elemental silver fibers or threads.

Highly sensitive silver halide emulsions, as are generally used for photographic recording and Reproduction purposes are known to have light-sensitive silver halide crystals active susceptibility centers or sites believed to be tiny silver sulfide aggregates contain the sulfide content either naturally in the polymer matrix, for example

se comes from a gelatin matrix, contains active sulfur or is specially added during production. A limited but effective number of such sensitivity centers should be used for optimal sensitivity or sites are present in each crystal, in particular on the surface of the crystals. When exposed with incident for the crystals of actinic electromagnetic radiation is believed to be that of Crystalline absorbed photons within the crystals generate photoelectrons which lead to the one Sensitivity centers having lower conductivity band level can diffuse and these Centers are provided with a negative charge, which in turn forms a precipitate originally in the crystal lattice effect of free silver ions present as elemental silver at the sensitivity centers. In the subsequent development of the exposed silver halide crystals is provided by the silver halide developer which is a reducing agent, additional electrons, which the precipitation of further Silver ions of the crystals cause what leads to the outgrowth of fibrous or filamentary elementary elements Silver structures at the surface sensitivity centers lead to complete reduction the crystals continues. In this context, the older DE-OS 20 36 213 is based on the knowledge that that the presence of the silver precipitation nuclei immediately adjacent to the silver halide crystals in of the emulsion during the development process the formation of the microscopic fibrous or filamentary Outgrowths of elemental silver on the crystal surfaces are effectively prevented and thus the Grain size of the (negative) image silver obtained, and thus the opacity of the negative silver image, on the Dimensions of the original crystals dispersed in the photosensitive matrix are limited without the As with the usual negative images, there is a subsequent amplification by increasing the Diameter comes as a result of fiber or thread-like image silver structures.

In order to ensure the desired generation of a positive image with high opacity, according to the older DE-OS 20 36 213 underlying knowledge the silver precipitation nuclei in the light-sensitive Silver halide emulsion arranged in such an effective concentration per unit area that ensures that (positive) image silver derived from unexposed silver halide crystals at the same time the desired (high) opacity per unit mass of silver reduced in situ through the storage of silver precipitate germs in the effective concentration mentioned in the Emulsion layer itself achieved advantages in the in-situ precipitation of negative silver with less Opacity and image density and the simultaneous also in-situ precipitation of the positive image silver in the same Layer with high opacity and high image density is shown in FIGS. 2 to 6 of the older DE-OS 20 36 213 referenced.

The incorporation of development nuclei for positive image formation in the emulsion layer of one after the recording material working with the Sflbersalzverfahren is as such, for example, from the German Patent 9 03 531 or the Belgian patent 5 45 678 known per se, however, without deriving the possibility and the special conditions for the Generation of the positive surface with extremely high Opacity relative to the negative image would be inferred.

Overall, according to the proposal of the older DE-OS, the light-sensitive silver halide crystals the emulsion layer in a silver precipitate

<, containing environment, ensures during development in the presence of a silver halide solvent that exposed silver halide grains are reduced to opaque structures with a smaller cross-sectional area than during development

in the same silver halide grains with the same silver halide solvent-developer composition, but without such developer seeds; has image silver derived from exposed silver halide grains therefore a lower optical opacity compared to the opacity of identical and equal Wise developed grains in the absence of the precipitation environment. The direct positive sil Image of macroscopically essentially uniform, but microscopically non-uniform distribution has a permeability depending on the amount or intensity of the exposure to the photosensitive silver halide used actinic radiation. The exposed silver halide grains are reduced in situ as compact masses with the mentioned low opacity, and at the same time are, also in situ, unexposed silver halide grains as colloidal dispersions of high covering power reduced. This is done in this way by in-situ deposition in the photosensitive layer itself The direct positive silver image produced has an extraordinarily high sharpness compared to the usual Silver salt diffusion transfer process in which unexposed silver halide grains are dissolved and passed through Diffusion are transferred into the ultimately image-bearing image-receiving layer.

The invention is thus based on an integral recording material of the type mentioned at the beginning according to DE-OS 20 36 213, in which under the specified conditions (application of a light-sensitive Emulsion layer containing silver halide crystals at a certain concentration silver precipitation nuclei and development in the presence of a silver halide solvent) in the photosensitive Emulsion layer itself a positive silver image with high opacity through in-situ deposition (i.e., high image density based on a given amount of reduced silver per unit area) is, while at the same time developing the negative image present in the same layer on an extremely low opacity and therefore despite the overlay with the positive image this when viewed nichi influenächiigi, especially holiness the highlight areas (which correspond to the areas of maximum blackening of the negative image) not noticeably reduced The material can be used before, during and after the exposure and Developing treatments are maintained unseparated as composite image material; through in-situ generation of the positive silver image, this is characterized by an extraordinarily high degree of sharpness, in Compared to the silver salt transfer process, which is otherwise closest to the mechanism; a Such a silver salt recording material with in-situ generation of positive and negative images in the same Layer is suitable because of the high level of diffusion achieved by largely avoiding lateral diffusion Sharpness in particular for training as a color photographic recording material in connection with

an additive color raster for recording exposure permanently integrated into the recording material and playback.

From a recording material of this type mentioned in the older DE-OS 20 36 213 ί On the basis of the present invention, the object is a further improvement with regard to the density difference between positive and negative image while maintaining the high image sharpness.

The object is achieved in that κι is directly adjacent to the light-sensitive emulsion layer a light-insensitive layer containing silver precipitation nuclei is provided.

The invention is based on the surprising finding that in a recording material the initially mentioned type according to the older DE-OS 20 36 213, d. H. a silver salt recording material with positive imaging in situ in the photosensitive silver halide layer, even better results can be achieved if immediately adjacent to the silver halide crystals and silver precipitation nuclei light-sensitive layer containing a per se light-insensitive, but also silver precipitation nuclei containing layer is provided. This results in the desired formation of the negative and Positive silver images with widely differing opacity are still improved or achieved that from the Composite image consisting of positive and negative images superimposed on one another particularly low values of minimum image density in the exposed areas of the film unit and especially has high values of maximum image density in the non-exposed areas It can be assumed that that also in the case of the recording material according to the invention, in which thus in addition to the light-sensitive and a further layer containing silver precipitation nuclei, however, which is insensitive to light as such layer also containing silver precipitation nuclei is present, through the substantial positive image formation Silver precipitation takes place in situ, thus the invention provided additional light-insensitive, silver precipitation nuclei-containing layer essentially as a precipitation catalyst for the positive silver precipitation in situ in the near-surface areas of the photosensitive layer acts as it is essentially a positive image generation in-situ precipitation without significant lateral diffusions of the components producing the positive image acts, results in the recording material according to the invention also an extremely high image sharpness.

According to preferred embodiments of the invention it can be provided that the silver precipitation nuclei are present in the photosensitive layer in such a concentration that a minimum image density of not more than 0.5 and preferably of not more than 0.3 and a maximum image density of not less than 1.5, and preferably not less than 1.8. In other words, according to these preferred embodiments, a density difference of at least 1.0 and preferably of at least 1.5 density units between the predetermined maximum image density of the developed negative silver image, ie then, and the predetermined minimum image density of the developed positive silver, ie Dam, can be achieved.

In detail, according to preferred embodiments, the film unit can be manufactured so that completely exposed areas of the silver halide layer during development have a maximum silver image density of less than about 0.5, and preferably less than about 0.3, and the silver precipitate nuclei can in such a concentration should be provided that unexposed areas of the silver halide layer in the Development treatment has an image density of at least about 1.0, preferably at least 1 and particularly preferably of more than 2.0 or even 3.0 density units. According to preferred Refinements can be provided that the silver halide layer sensitized panchromatically Contains silver iodochlorobromide or silver iodobromide, preferably with a content of 1 to 9% by weight Iodide based on the silver, dispersed in a permeable colloidal binder, preferably sufficiently hardened gelatin with a hydration factor, that upon contact with a preferably having a pH greater than about 12 aqueous treatment liquid causes excessive swelling within a period of up to about Effectively prevented for 15 seconds.

According to particularly advantageous embodiments, it can be provided that on the free surface of the a second layer, insensitive to light, containing silver precipitation nuclei and silver halide solid solutions photosensitive layer is located, and that the photosensitive emulsion layer is between two light-insensitive, silver precipitation nuclei containing layers is located.

Due to its advantageous properties (high positive image sharpness with very different optical Density of the positive and negative images in overlap in the composite image) is suitable material according to the invention preferably for training as a color photographic recording material per se known permanent integration of an additive color grid with the composite image recording material. A preferred such color photographic embodiment may take the form of a film unit in the form a permanently firmly connected laminate be formed on one surface of an additive Farbrasters a first photosensitive emulsion layer containing silver halide and silver precipitation nuclei a light-insensitive layer containing silver precipitation nuclei and a second, silver halide and a photosensitive emulsion layer containing silver precipitates.

According to an advantageous embodiment of the invention it is provided that the light-insensitive, Layer containing silver precipitation nuclei has a thickness of preferably less than about one wavelength of the Having exposure radiation; 11m any side Diffusion of the components forming the positive image during the processing of the film unit to reduce as much as possible.

In the following, exemplary embodiments of the invention are described with reference to the drawing; in this shows

1 shows a schematic, enlarged cross-sectional view of a recording material according to the invention, with the thickness of the various layers being exaggerated

F i g. 2 in the F ϊ g. 1, a schematic, enlarged cross-sectional view corresponding to another embodiment of the invention that

Figures 3 and 4 in Figures 1 and 2, respectively corresponding schematic, enlarged cross-sectional view of further embodiments of the Eifin-

dung that

5 to 8 each in a schematic, enlarged Cross-sectional view of particularly preferred embodiments of the recording material according to the invention in the form of a color photographic one Recording material.

The recording material according to FIG. 1 comprises a flexible, transparent support 10 which has the following layers on one of its surfaces in the order given: a photosensitive silver halide layer 11, which has silver precipitation nuclei dispersed throughout the layer, and a substantially light-insensitive layer 12 which also contains silver precipitation nuclei.

In the case of designs with a color screen, the light-sensitive silver halide emulsion layer becomes preferably arranged directly adjacent to the color raster in order to avoid possible optical parallax problems when the radiation passes through, as well as the mentioned lateral diffusion of silver image-forming components during to reduce the development treatment of the recording material as much as possible.

In a preferred embodiment of the invention according to FIG. 2, the light-insensitive layer 12 is arranged between the layer support 10 and the light-sensitive layer 11. In the case of the in FIG. Embodiment shown in Figure 3 are two separate and distinct light-insensitive layers 12 in each case immediately adjacent to the opposite surfaces of a photosensitive layer 11. The marking material shown in Figure 4 comprises comprises a flexible transparent substrate 10, the following on a surface in the order given layers : a first photosensitive layer 11 containing photosensitive silver halide crystals and silver precipitating nuclei, a substantially photosensitive layer 12 containing silver precipitating nuclei, and a second photosensitive layer 11 containing photosensitive silver halide crystals and silver precipitating nuclei.

The recording material according to FIG. 5 comprises the following layers on a flexible, transparent support 10 in the order given: an additive color raster 14, which has a geometrically repeating arrangement of a multiplicity of actinic radiation-filtering colored elements, namely red-colored, blue-colored and of green-colored filter elements which are arranged essentially in one plane next to one another in a repetitive distribution; a photosensitive silver halide layer 11. containing silver precipitating nuclei dispersed throughout the layer; and a layer IZ containing essentially light-insensitive silver precipitation nuclei

In the preferred embodiment of the invention shown in FIG. 6, the light-insensitive one Layer 12 arranged between the color raster 14 and the photosensitive layer 11 in FIG. 7 are two separate and separate light-insensitive layers 12 are shown, which are attached to the two Sides of a photosensitive layer 11 are in contact.

The particularly preferred recording material shown in FIG. 8 comprises the following layers on a flexible, transparent layer support 10 in the order given: an additive color raster 14, a first light-sensitive layer 11 which contains light-sensitive silver halide crystals and precipitating nuclei, and a substantially light-insensitive silver precipitating nuclei Layer 12, as well as a second light-sensitive layer 11, which contains light-sensitive silver halide crystals and silver) precipitation nuclei.

As already mentioned, the photosensitive layer 11 preferably contains crystals of a silver compound, for example one or more silver halides, such as photosensitive silver chloride, silver iodide, silver

Ki bromide, and in particular mixed silver halides, such as Silver chlorobromide, silver chloroiodobromide or silver iodobromide with changing halide ratios and silver concentrations, each preferably in a binder material permeable to the developer

i-> dispersed. This binding material also contains Silver precipitation nuclei dispersed throughout the emulsion in a concentration that depends a strong deposition or precipitation of elemental silver in the

3d causes unexposed areas of the emulsion, and with a very high opacity compared to the exposed areas of the emulsion.

The silver precipitation nuclei or nuclei are known to be a class of auxiliary substances which

2 ^r , effect a catalytic reduction of solubilized silver halide. This class includes in particular heavy metal compounds such as metals from groups Ib, Hb, IVa, VIa and VIII and reaction products of metals from group VIa. she

so are used in the usual concentrations, preferably in a relatively low concentration of about 1 to 25 · 10 ~ ⁶ mol / 0.09 m ² .

Particularly suitable silver precipitation nuclei or cores are described in US Pat. No. 2,698,237. It are specifically metal sulphides and selenides, which also include selenosulphides, the polysulphides and the Polyselenides belong. Heavy metal sulfides are preferred. From this group are preferred Sulphides used, their solubility product in one

4 (in an aqueous medium of about 20 ^° C. between 10- "and ^10-30 , in particular the salts of zinc, copper, cadmium and lead. Heavy metals such as silver, gold, platinum and palladium are also particularly suitable as overprecipitation nuclei Noble metals are preferred and are generally contained in the matrix as colloidal particles.

The silver halide photographic emulsion is prepared in the usual manner. You can use sensitizers and other common additions included.

As a binder for the photosensitive recording material, the gelatin which is preferably used can be wholly or partly replaced by another natural and / or synthetic for the developer or. Treatment liquid permeable polymeric material such as albumin, casein or zein can be replaced by resins such as cellulose derivatives (US Pat. Nos. 23 22 085 and 25 41 474) or by vinyl polymers. Further examples of suitable, essentially binder-free photosensitive materials can be found in US Pat. Nos. 29 54 771, 31 45 566, 31 42 567, the publication by Newman, Comment on Non-Gelatin Film, BJOP, 534.15. Sept 1961 and Belgian patents 6 42 557 and 6 42 558.

To make the separate discrete

Layers) 12 of precipitated germs can be found in Proceed in such a way that you can remove the precipitate directly or indirectly directly on one or both surfaces of the photosensitive layer with or without

Applies, arranges and / or generates binder in situ. In the case of application without a binder can this layer consists of one or more adjacent or separate layer (s) of a permeable Material exist, wherein the precipitation nuclei can be in one or more of these layers. One or more different types of silver precipitate nuclei can be used. Suitable as a binder both inorganic and organic materials, the latter being preferred for the treatment liquid permeable, natural or synthetic polymeric materials, such as proteins, for example Glues, gelatine or caseins, carbohydrates, for example chitins, gums, starches or alginates, synthetic polymers, for example vinyl or cellulose polymers such as vinyl alcohol, vinyl amides and Acrylamides, regenerated cellulose and cellulose ethers and esters, polyamides and polyesters. examples for inorganic binders are sub-macroscopic agglomerates of small particles of a water-insoluble, inorganic siliceous material such as colloidal silica (US Pat. No. 2,698,237).

If one or more heavy metal sulfides or selenides are used as silver precipitation nuclei, should to prevent diffusion and migration of the sulfide or selenide ions in the silver precipitating Layers or at least one metal salt are provided in separate layers closely adjacent to them, which is much more soluble in the treatment liquid than the metal sulfide or selenide and which is not reducible by the treatment composition. This more soluble salt has than Cation on a metal, the ion of which forms sulfides or selenides, which are difficult to use in the treatment composition are soluble and release their sulfide or selenide ions by exchanging them with silver. Therefore the Metaliionen of the more soluble salts in the presence of sulfide or selenide ions that they are the sulfide or Instantly precipitate selenide ions from solution. These more soluble salts can be soluble salts of the be the following metals; Cadmium, Cer- (III), Cobalt- (II), Iron, lead, nicke !, manganese, thorium and tin. A! S soluble and stable salts of these metals are suitable for example their acetates, nitrates, borates, chlorides, sulfates, hydroxides, formates, citrates and dithionates. The acetates and nitrates of zinc, cadmium, nickel and lead are preferred and are generally colorless or weakly colored salts, albeit dark colored salts for certain special purposes can be used.

The mentioned more soluble salts can also improve the stability of the positive image serve, provided that they meet the properties already mentioned in that of the US patent 25 84 030 have specified properties. For example, if the more soluble salt is slow insoluble or sparingly soluble metal hydroxides with the hydroxyl ions in the alkaline treatment liquid forms, it will suitably control the pH of the recording material so that the formation of undesirable Developer stains is largely or even completely avoided.

According to a particularly preferred embodiment of the invention, the photosensitive section and the image receiving portion carrying the silver image formed so that in order to avoid microscopic Shift or distortion of image details a microscopic migration or

Diffusion of image details within the polymer matrix is prevented. In general, can common photographic picture elements normally contain a microscopic dynamic system without that this would result in serious disadvantages in the normal use of the picture. For one special however, exact information recording should allow for a microscopic displacement or distortion of Image elements are preferably avoided in order to achieve maximum accuracy of the image reproduction, and, in the case of color reproduction, precise alignment of the image with the appropriate individual optical To ensure silver elements with the additive color raster assigned to the image carrier element. In particular it was found that a recording material, which photosensitive emulsion with a Content of silver halide crystals and silver precipitation nuclei dispersed in a polymeric binder and a light-insensitive silver precipitate is dispersed in a polymeric binder containing image-receiving layer, wherein the binders have an internal structure which is a effectively prevents microscopic migration or diffusion of image silver, which is particularly important for color photographic recording leads to the desired high sharpness of image reproduction. The desired one The lattice structure of the binder can be determined in a simple manner by selecting a polymeric binder achieve, which has the property of fixing image components sufficiently in space, or can be a certain desired polymeric material are modified by crosslinking and / or curing so that the positive image components to the individual optical filter elements of the color grid through which the light-sensitive emulsion has been exposed, are assigned sufficiently rigid-immobile. For example The preferred polymeric binder, gelatin, can be combined with conventional hardening agents to achieve the desired rigidity of the photographic image can be sufficiently hardened. If necessary, can particulate materials that increase the penetration of the processing liquid into the photosensitive Ensure section without impairing the lattice structure of the polymer matrix in the photosensitive Layer incorporated to support the development treatment of the recording material will.

The substrate 10 can be any of a number of known transparent, rigid, or act flexible carrier materials, z. B. glass or a polymer film natural or synthetic Origin. Particularly suitable materials are flexible, clear synthetic polymers such as Polymetharyl acid methyl and ethyl ester; Vinyl chloride polymers; Polyvinyl acetates; Polyamides such as nylon; Polyesters derived from ethylene glycol therephthalic acid; polymeric cellulose derivatives such as cellulose acetate, triacetate, nitrate, propionate, butyrate, acetate butyrate or acetate propionate; Polycarbonates; Polystyrene.

Specific examples of the present invention will now be described Recording materials described.

example 1

^{A composition of 3.75 mg / 0.09 m 2 of} gelatine, 3.75 mg / 0.09 m ^{2 of} deacetylated Chidn and 0.7 nig / 0.09 m ^{2 of} diaminoortho was applied to a cellulose triacetate layer support coated with gelatine as a base - Eaten cresol. On the outer surface

Before the gelatin layer, a hardened gelatin-silver iodobromide emulsion was poured on, which contained cadmium sulfide and silica, with a coverage of 200 mr / 0.09 m ² gelatin, 100 mg / 0.09 m ² silver, 0.97 mg / 0.09 m ² cadmium sulfide, 0.026 mg / 0.09 m ² chrome alum, 0.78 mg / 0.09 m ² algin and 200 mg / 0.09 m ² silica. The material thus obtained was then coated with a layer of 3 mg / 0.09 m ² deacetylated chitin and 1 mg / 0.09 m ² copper sulfide.

The gelatin-silver iodobromide emulsion was prepared by heating a mixture of 80 g gelatin in 880 g Water at 40 ° until the gelatin dissolved. The pH of the solution was adjusted to 10 ± 0.1 and 8.8 g of phthalic anhydride in 61.6 ml of acetone were added to the solution in the course of 30 minutes. Then became the reaction mixture for about 30 minutes at the indicated values of temperature and pH attained and finally to a pH of about 6.0 set

To a solution of 226 g of the gelatin-phthalic anhydride derivative prepared as described above 161 g of potassium bromide, 2 g of potassium iodide and 1200 g of water and a solution are added, which contained 200 g of silver nitrate in 1600 g of water. The addition is carried out at a rate of about 140 ml per minute, over the course of about 30 minutes, then held the whole IC minutes and then the Addition continued for about 9 minutes. The resulting emulsion was then made up by lowering the pH to about 2.5 to 3.0 precipitated with sulfuric acid, the precipitate from the liquid above separated and washed with water until the wash water is practically free of excess potassium bromide was. 95 g of gelatin were then added to the precipitate, making up the volume with water 845 ml and made up by heating to about 38 ° in the course of about 20 minutes at a pH of 5.6 dissolved, with the emulsion about 1.0 ml of n-potassium bromide was admitted. This reaction mixture was at 56 ° with about 5 ml of a solution containing 0.1 g of ammonium thiocyanate in 9.9 ml of water, and with 0.4 ml of a solution containing 0.097 g of gold chloride in 9.9 ml of water contained, added. The mixture was ripened at this temperature for about 37 hours. the The resulting emulsion was panchromatically sensitized by successive addition of: 0.1% by weight methanolic solutions of anhydro-5,5'-diphenyl-3,3'-bis (4-sulfobutyl) -9-ethyl-oxycarboxy- anine hydroxide and anhydro-5'-dimethyl-3,3'-bis (3-sulfopropyI) -9-ethyl-thiocarboxyanine hydroxide. To the panchromatically sensitized Süberiodobromide emulsion obtained in this way were cadmium sulfide as a silver precipitation nuclei or agent before potting added, in situ by adding approximately equimolar amounts of cadmium nitrate and sodium sulfide solutions was formed as well as the porosity causing silicon dioxide and the anti-swelling agent.

The recording material of the present invention obtained in the above manner was subjected to the exposed transparent substrate. The recording material was developed for 2 seconds with a Contacting treatment composition containing 180 ml of water, 8.33 g of sodium hydroxide, 16 g Sodium thiosulfate, 6.48 g sodium sulfite, 0.42 g 6-nitrobenzimidazole and contained 5 g of 2,6-dimethylhydroquinone. A positive silver image was obtained with the above described advantageous properties and an excellent image sharpness.

The recording material developed showed an Ömax silver coverage of 89.8 mg / 0.09 m ² and a D _mm - S coverage of 89.8 mg / 0.09 m ² and an optical density of 1.80 and 035, respectively.

For comparison, a recording material was produced with the same layer structure, but with the important difference that the light-insensitive layer according to the invention with the silver precipitation nuclei was omitted. It was among the

ίο developed under the same conditions This comparison image showed an Amw silver coverage of 89.5 mg / 0.09 m ² and a D _OT uj silver coverage of 89.5 mg / 0.09 m ² as well as an optical density of 130 or 0, 35.

According to the above manufacturing and development

With the recording materials according to the invention, values of D _mix of 33 and D _m i n of 0.3 can be achieved with the recording materials according to the invention, ie with a density difference of 3.0 corresponding to a percentage transmission ratio of about 1000: 1.

If necessary, due to certain selected color grid properties, values D _max of 4.0 and Dmin of 0.3 can be achieved, ie a density difference of 3.7 corresponding to a percentage transmission ratio of about 5000: 1.

Example 2

Another recording material was produced as follows: A hardened gelatin-silver iodobromide emulsion containing cadmium sulfide and silica with 100 mg / 0.09 m ² gelatin, 50 mg / 0.09 m ² silver, 0 , 49 mg / 0.09 m ² cadmium sulfide, 0.013 mg / 0.09 m ² chrome alum, 0.39 mg / 0.09 m ² algin and 100 mg / 0.09 m ² silica poured on. A layer containing 3 mg / 0.09 m ^{2 of} deacetylated chitin and 1 mg / 0.09 m ^{2 of} copper sulfide was then applied to the outer surface of the emulsion layer. This recording material was then coated with a hardened gelatin-silver iodobromide emulsion containing 100 mg / 0 , 09 m ² gelatin, 50 mg / 0.09 m ² silver, 0.49 mg / 0.09 m ² cadmium sulfide, 0.013 mg / 0.09 m ² chrome alum, 0.39 mg / 0.09 m ² algin and 100 mg / 0.09 m ^{2 of} silica.

After the development treatment, this recording material showed a D _ra "silver coverage of 114.7 mg / 0.09 m ² and a D _m ," silver coverage of 114.7 mg / 0.09 m.? and an optical density of 2.19 and 0.31, respectively.

For comparison, only the last-mentioned second light-sensitive silver iodobromide emulsion layer has been omitted from a comparative recording material of the same type and treated in the same way. It had a Z) _ma r silver coverage of 89.8 mg / 0.09 m ² , a D _m ; „- silver coverage of 89.8 mg / 0.09 m ² and an optical density of 1.80 and 0.35, respectively . Recording material which, in addition, had no separate layer _{according to the invention, containing essentially light-insensitive silver precipitation nuclei, had the following values: D m} "silver coverage of 89.8 mg / 0.09 m ² , a D _m " silver coverage of 89.8 mg / 0.09 m ² and an optical density of 1.30 and 033, respectively.

In this case, too, according to the above manufacturing and development information, with inventive

b5 according to the invention, under optimized conditions, values D _m , _x of 3.3 and D _m , "of 0.3, ie. a density difference of 3.0 density units corresponding to a percentage

Transmission ratio of about 1000: 1. If necessary, on the basis of certain selected color grid properties, values D «, of 4.0 and Dam of 03 can be obtained, ie a difference of 3.7 density units corresponding to a percentage transmission ratio of about 5000: 1.

The color grid 11 can be according to any one of known processes are produced, which are generally purely mechanical and photomechanical or collotype printing.

Color raster production can be done purely mechanically, for example by printing or lining a dyeable substrate, e.g. B. with a greasy one Printing color according to the desired filter pattern and subsequent coloring of the non-printed th areas, repeated for each filter color, take place. An alternative method consists in successive direct printing of the desired Color approaches on a layer support according to the predetermined filter pattern. Another mechanical one The method consists in the deposition of an irregular filter grid pattern as a thin layer. with a Random distribution of smaller bodies colored independently of one another with the desired filter colors, for example starch granules.

In the photomechanical color raster manufacturing process using collotype printing, the Usually a light-sensitive gelatin layer, for example sensitized with bichromate, poured onto a layer support through one of the desired layers The corresponding mask is exposed through the arrangement of the optical filter elements; the exposed areas of the Materials are hardened, while the unexposed non-hardened material with a solvent Will get removed; the remaining hardened material corresponding to the exposed areas then becomes colored with the desired filter color and the same procedure for the other filter colors Filter elements repeated.

Although the production of the color grid 11 can in principle be carried out according to any of these known methods, experience has shown that the photomechanical process because of the low production costs and the better accuracy for the Mass production of color grids with the optical accuracy required for commercial purposes are preferable to the purely mechanical process.

The photomechanical production of color grids using so is particularly advantageous Lenticular lens film as described in US Pat. No. 3,284,208. Here, a lenticular lens film becomes consecutive on its smooth surface coated with several photosensitive layers and the coatings each one exposure with selective subjected to radiation displaced by the lenses. After each exposure, the unexposed part of the coating removed and the remaining part colored and so a series chromatic filter elements generated before the after- f> o ste light-sensitive layer is applied.

The respective depth of the linear exposure of the photosensitive layers can be varied precisely control the intensity or exposure time; the color raster obtained can be continuous or tn be discontinuous.

To produce the preferably used trichromatic additive screen, the exposure is in each case The th area of each photosensitive area is generally about V3 that of each lens of the lenticular lens adjacent layer The three exposures can each be viewed through at three different angles the lenses of the lenticular film of incident radiation take place; however, a chromatic filter can also be used by exposing the light-sensitive layer to light Reach diffuse radiation through the lenticular lens film, with the help of the masking effect of the previously generated color filter elements. If necessary, one or more of the during exposure The image groups formed overlap in order to reduce or reduce fluctuations in the width of the exposed areas. balance.

One particularly suitable for exposing a lenticular lens film according to US Pat. No. 3,284,208 Apparatus is described in US Pat. No. 3,318,220.

The production of a recording material according to the invention with an integrated color raster, which according to the aforementioned photomechanical method using a lenticular lenticular film is explained in the following example.

Example 3

The starting point was a lenticular lens film in the form of a polyester carrier which was provided on one surface with a cellulose acetate butyrate layer with 550 lenses / 2.54 cm. The lenses were plano-convex with a focal length of about 100 μ in air. As a result of this short focal length, objects were imaged at a distance of up to about 2.54 cm from the lens surface at infinity. which contained 70 ml of methanol, 1.25 g of nitrocellulose and 30 ml of butyl alcohol. A first gelatin layer sensitized by adding 15% by weight of potassium dichromate (based on dry gelatin) was then applied to the outer surface of this first adhesive layer exposed to UV radiation explained above and the exposed support obtained in this way washed with water in order to remove unexposed sensitized gelatin in accordance with the exposure pattern contained in the first gelatin layer. The reticulated or lattice-shaped pattern was then treated with an acid dye bath containing 1.17% red dye CI. 81; 032% yellow dye CI. 4; and contained 2.95% glacial acetic acid. Excess dye was then washed off, the whole thing dried, and a coating of a second adhesive material was applied which contained 70 ml of methanol, 30 ml of butyl alcohol and 1.25 g of nitrocellulose. A second gelatin layer, sensitized by adding 15% by weight of potassium dichromate, was poured onto this second adhesive layer; the second photosensitive gelatin layer was also exposed to UV radiation and washed with water to remove unexposed photosensitive gelatin. The remaining part of this gelatin layer was then stained with an acid dye bath, the 0.83% green dye CI. 7; 032% yellow dye CI. 4 and 2.86 ° / o glacial acetic acid. The net-like or lattice-like arrangement obtained in this way was then again used

Removal of excess paint, washed, dried and coated with a third adhesive, the 30 ml of butanol, 1.25 g of nitrocellulose and 70 ml of methanol A third adhesive layer was finally applied to the outer surface of the third adhesive layer at 15% by weight / c Potassium dichromate sensitized gelatin layer applied and exposed to UV radiation Exposure, this third photosensitive gelatin layer was washed again and the remaining layer Gelatin stained with a solution that is 1.0% blue Dye and 1% glacial acetic acid, followed by washing to remove excess dye. Finally, a protective coating was applied to the outer surface of the multicolored screen element obtained poured from 70 ml of methanol, 30 ml of butanol and 5 g of nitrocellulose.

After the color grid has been produced, the lenticular layer made of cellulose acetate butyrut can be removed from the polyester base and a mass poured onto the outer surface of the protective polymeric coating which deacetylated 3.75 mg / 0.09 m ² gelatin, 3.75 mg / 0.09 m ² chitin and 0.7 / 0.009 m ² diamino-orthocresol contained on the external surface of the gelatin layer was a hardened gelatin-silver iodobromide emulsion applied, the 200 mg / 0.09 m ² of gelatin, 100 mg / 0,09 m ² silver, 0 , 97 mg / 0.09 m ² cadmium sulfide as silver precipitation nuclei, 0.026 mg / 0.09 m ² chrome alum, 0.78 mg / 0.09 m ² algin and 200 mg / 0.09 m ² silicon dioxide. The recording material thus obtained was coated with a layer which contained 3 mg / 0.09 m ^{2 of} deacetylated chitin and 0.1 mg / 0.09 m ^{2 of} copper sulfide

The gelatin-silver iodobromide emulsion was prepared and sensitized as described in Example 1 above.

The resulting inventive color photographic recording material with an integrated color raster was exposed and for about 2 seconds with a Treatment liquid developed which contains 180 ml of water, 8.33 g of sodium hydroxide, 16 g of sodium thiosulphate 6.48 g Sodium sulfite, 0.42 g 6-nitrobenzimidazole and 5 g 2,6-dimethylhydroquinone. One obtained here a positive silver image with the advantageous optical properties described above and for additive color rendering required accuracy

The recording material developed showed a D _m "silver coverage of 89.8 mg / 0.09 m ² , a D _min silver coverage of 89.8 mg / 0.09 m ² and an optical density of 1.80 and 0, respectively. 35

For comparison, a similar recording material was produced and developed in the manner described above, but with the difference that the layer containing separate silver precipitation nuclei was omitted. The resulting image showed a £) _{m4X silver} coverage of 89.5 mg / 0.09 m ² and a D _{m /} >, silver coverage of 89.5 mg / 0.09 m ² as well as an optical density of 130 resp. 033.

According to the production and development information given above, when optimized, color photographic recording materials according to the invention can achieve values D _mu of 33 and D _m i ” of 0.3, ie density differences of 3.0 corresponding to a percentage transmission ratio of about 1000: 1. If necessary, for example, due to certain selected color grid properties, values D _mu 4.0 and D _m , ”of 03 can be achieved, ie density differences of 3.7 corresponding to a percentage transmission ratio of about 5000: 1.

Example 4

According to a particularly preferred embodiment, after the formation of the color screen, the cellulose acetate butyrate lens screen layer can be removed from the polyester layer support and the outer surface of the polymeric protective coating coated with a hardened gelatine-silver iodobromide emulsion containing 100 mg / 0.09 m ² gelatine, 50 mg / 0.09 m ² silver, ίο 0.49 / 0.09 m ² cadmium sulfide, 0.013 mg / 0.09 m ² chrome alum, 039 mg / 0.09 m ² algin and 100 mg / 0.09 m ² silica. A light-insensitive layer according to the invention can then be applied to the outer surface of the emulsion layer, which layer contains 3 mg / 0.09 m ^{2 of} deacetylated chitin and 1 mg / 0.09 m ^{2 of} copper sulfide as silver precipitation nuclei. This recording material can then be coated with a hardened gelatin-silver iodobromide emulsion are coated, the 100 mg / 0.09 m ² gelatin, 50 mg / 0.09 m ² silver, 0.49 ^{mg / 0.09 m 2} cadmium sulfide as silver precipitation nuclei, 0.013 mg / 0.09 m ² chrome alum, 039 mg Contains / 0.09 m ² algin and 100 mg / 0.09 m ^{2 silica}

This recording material was exposed through the transparent support and developed for about 2 seconds with a treatment liquid containing 180 ml of water, 833 g of sodium hydroxide, 16 g of sodium thiosulfate, 6.48 g of sodium sulfite, 0.42 g of 6-nitrobenzimidazole and 5 g of 2,6-dimethylhydroquinone The positive silver image obtained in this way, with a high sharpness corresponding to the requirements of additive color photography, showed a D _{ma; r} silver coverage of 114.7 mg / 0.09 m ² and a D mm silver coverage of 114.7 mg / 0.09 m ² as well an optical density of 2.19 and 0.31, respectively.

A comparison material prepared as described above and treated for development, but in which the second light-sensitive silver _{iodobromide emulsion layer was omitted, showed a D m} "silver coverage of 89.8 mg / 0.09 m ² and a D _ra i" silver coverage of 89, 8 mg / 0.09 m ² and an optical density of 1.80 or 035. A recording material which had neither the second overlying photosensitive emulsion layer nor the separate, essentially light-insensitive layer containing silver precipitation nuclei according to the invention showed a D / mu Silver coverage of 89.8 mg / 0.09 m ² and a D _m , "- silver coverage of 89.8 mg / 0.09 m ² and an optical density of 130 and 033, respectively.

According to the production and development treatment information given above, when optimized, color photographic recording materials according to the invention can achieve values D _mtx of 3.3 and D m of 0.3, ie density differences of 3.0 corresponding to a percentage transmission ratio of about 1000: 1. If necessary, due to certain selected color grid properties, values D _m "of 4.0 and D _m /" of 03, ie density differences of 3.7, can be achieved, which corresponds to a percentage transmission ratio of about 5000: 1.

The recording materials according to the invention are particularly suitable for use as a cinema film and as a slide film because it can be subjected to a simple developing treatment immediately after exposure can be subjected without having to separate the emulsion layer from the rest of the recording material.

According to the information in the examples, the light-sensitive silver halide emulsion and / or the layer containing silver precipitates are advantageous

contain particulate materials that form these layers without impairing dimensional stability give the binder lattice increased porosity and also act as anti-swelling agents, which any microscopic displacement or distortion of the image structure, especially relative to the Avoid color raster. When using particulate silica dispersed in the binder their concentration is, for example, about 03 to 1.5 parts of silica per part of binder. The emulsion layer that is remote from the color grid layer or layer containing silver precipitation nuclei can advantageously be combined with one for the treatment liquid permeable polymeric material, such as hardened gelatin. ι>

Suitable silver halide solvents are customary fixing agents, such as sodium thiosulfate, sodium thiocyanate, Ammonium thiocyanate, as well as the other substances described in US Pat. No. 25 43 181 are described, furthermore, combinations of cyclic imides and nitrogen-containing bases, such as barbiturates or uracils and ammonia or amines (U.S. Patent 2,857,274).

The treating composition generally contains an alkaline material, e.g. B. Sodium Hydroxide, Potassium hydroxide or sodium carbonate, especially at a concentration that suits the composition pH greater than 12 confers. The treatment composition may be the sole) silver halide developing agent (s) or, if necessary, it can additionally contain a silver halide developer substance be arranged in the recording material. The developer liquid can also contain conventional additives such as Contains preservatives, alkalis, silver halide solvents, retarders or accelerators.

In the preceding description it was indicated that each color row of filter elements V3 occupies the entire area, however, this can vary widely before the viewer has one visible effect and can also be compensated by changing the intensity of the colors, and Conversely, if one dye has a greater intensity than the others, it can do so be compensated by reducing the relative proportion of the more intense dye in the total area

Various colors can be used for the color photographic embodiments of the invention as well different numbers of colors can be used, but the preferred system is a three color arrangement with the three primary colors red, green and blue. However, a four-color system such as red, green, Violet blue and orange yellow can be used.

For the color photographic embodiments of the present invention, additive trichromatic Color raster with 550.756 and 1100 lines / color / 2.54 cm can be used. A better image resolution is achieved here than with the usual diffusion transfer processes is achievable in which a substantially complete transfer of the the image generating components is required on the image-receiving layer adjacent to the color raster.

The recording material according to the invention can in addition to the cited essential layers of course also contain one or more intermediate layers, which in turn have one or more may contain several additives such as plasticizers.

For this purpose 2 sheets of drawings

Claims (12)

Patent claims: 1. Photographic recording material operating by the silver salt process, which in the form of a permanently maintained laminate on a layer support a photosensitive Has emulsion layer, which silver halide solid solution and contains silver precipitation nuclei in such a concentration that in the emulsion layer one of the unexposed when developed in the presence of a silver halide solvent Positive silver image of high opacity emerges from silver halide mixed crystals, whose optical density is inversely proportional to the imagewise exposure of the emulsion, thereby characterized in that immediately adjacent to the photosensitive emulsion layer (ti) one Light-insensitive ones containing silver precipitation nuclei Layer (12) is provided 2. Recording material according to claim 1, characterized in that the light-insensitive Layer (12) contains the silver precipitation nuclei in such a concentration that during development in the presence of a silver halide solvent, that of exposed silver halide mixed crystals outgoing negative silver image has a maximum density that is at least 1.0 density units less than the positive silver picture shows. 3. Recording material according to claim 1 or 2, characterized in that in the light-insensitive Layer (12) the silver precipitation nuclei are present in such a concentration that a a minimum image density of not more than 0.5 and a maximum image density of not less than 1.5 will. 4. Recording material according to claim 3, characterized in that in the light-insensitive Layer (12) the silver precipitation nuclei are present in such a concentration that a minimal Image density of not more than 0.3 and a maximum image density of not less than 1.8 is obtained. 5. Recording material according to one of claims 1 to 4, characterized in that on the Free surface of the light-insensitive layer a third light-sensitive layer, the silver precipitation nuclei and contains silver halide solid solution (Fig. 4). 6. Recording material according to one of claims 1 to 4, characterized in that the photosensitive emulsion layer is located between two layers containing silver precipitation nuclei (Fig. 3). 7. Recording material according to one of claims 1 to 6, characterized in that the light-sensitive emulsion layer additionally dispersed 0.3 to 1.5 parts of silica per part of binder contains. 8. Recording material according to one of claims 1 to 7, characterized in that the light-sensitive) layer (s) contains deacetylated chitin as a binder. 9. recording material are present according to one of claims 1 to 8, characterized in that the silver precipitation nuclei m 25 × 10 ^-6 mol / 0.09 in a concentration of about Ibis. ² 10. Recording material according to one of claims 1 to 9, characterized in that the Silver halide mixed crystals as silver iodobromide Crystals are present which contain 1 to 9 wt .-% iodide. 11. Recording material according to one of the claims 1 to 10, characterized in that the light-sensitive layers) have a density of less than approximately one wavelength of the exposure radiation has (have). 12. Use of the recording material according to one of claims 1 to 11 for the production of Color copies, characterized in that the laminate contains an integrated color raster (14)