DE2360944A1 - LIGHT SENSITIVE PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

Priority: December 7, 1972 U.S.A. No. 312 827

Light sensitive photographic recording material

In US Pat. No. 3,672,890, a composite photosensitive recording material is described which is particularly suitable for color photographic diffusion transfer processes for the production of reflection images and which contains several essential layers, to those in the include the following sequence: A dimensionally stable, for conspicuous radiation preferably opaque layer5 one or more silver halide emulsion layers each having a diffusion transfer dye image the resulting material is assigned5 a polymeric layer, capable of receiving a solubilized dye image forming and diffusing material; and a dimensionally stable one transparent layer. This recording material can be exposed to incident actinic rays and then developed by between the silver halide emulsion layer and the receiving layer, a developing solution and a Opacifier is introduced, which conspicuously reduces rays

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can flex; the opacifying agent is present in sufficient amount to cover the dye image-forming material, .as assigned to the silver halide emulsion

In a preferred embodiment, the composite contains light-sensitive recording material tearable container in which there is an alkaline developer solution with the opacifying agent, the container is rigidly arranged so that it extends transversely to a leading edge of the recording material to after application a compressive force to cause the container to have the developing solution between the opposing surfaces the image-receiving layer and the closest adjacent silver halide emulsion layer.

That between the receiving layer and the silver halide emulsion Distributed developer liquid penetrates the SiI-berhalide emulsion layers of the composite photosensitive material to carry out development of the latent images contained therein and resulting from the exposure. As a result of the Development of the latent images becomes the dye image resulting Material assigned to the corresponding silver halide emulsion layers individually as a result of point-by-point exposure the corresponding silver halide emulsion layers immobilized, resulting in an image-wise distribution of moving dye image. materials leads, which are transferred by diffusion to the receiving layer to produce the desired dye transfer image there to surrender. Means are provided in the recording material so that, after substantial dye image formation, in of the receiving layer the pH of the recording material from a first development pH at which the dye image forms Material is diffusible as a result of ..exposure, is converted to a second pH at which the transfer image Has increased stability, preferably

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• sr. -.

a sufficient proportion of the ions of an alkaline developer solution by diffusion on a polymer neutralizing Schient is transferred to the alkalinity of the recording material from a first alkaline developer pH to reduce to the second pH, at which the color is formed resulting material is essentially non-diffusible and wherein further transfer of dye image-forming material is substantially avoided.

• the transfer dye image which is generated by the opacifier _r the rind as a component of the developing solution between the receiving layer of the silver halide emulsion layer closest has been distributed by the reflection image, the transparent layer stable against · betrachtet- the background. The opaque vision so formed effectively covers off residual pigment image-yielding material that is retained in association with the silver halide emulsion layer after development.

U.S. Patent 3,415,644 states that the dimensionally stable layer of the recording material which closest to the photosensitive layer or layers should be opaque, with the opacifier from the beginning, is arranged in an aqueous: alkaline developer solution and means are provided with 'which the pH of the recording material are influenced can. These agents are polymeric Layer that is transparent between the dimensionally stable Sends and the receiving layer is arranged and the after substantial formation of a dye transfer image the. pH of the aqueous alkaline developing solution of one .first development pH at which the dye-forming elements

• Materials in the EntwieklerlÖsuttg as part of the exposure

■ the associated light-sensitive silver halide

■ layers are soluble and diffusible on a second pH decreased at which the paraffin image-forming material '

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is essentially not diffusible. U.S. Patent 3,415,646 states that the dimensionally stable Layer of the recording material which is closest to the one or more light-sensitive silver halide layers is transparent to incident actinic rays. U.S. Patent 3,415,645 is described that in such a pail the opacifier from the beginning in the recording material between the receiving layer and the closest silver halide layer can be arranged.

According to US Patents 3,615,421 and 3,661,585, the opacity component of the recording material can optionally be arranged from the beginning as a pre-formed layer permeable to the developer solution between the receiving layer and the closest silver halide layer in a concentration that is insufficient before exposure to the To prevent the exposure of actinic radiation from passing through, but has an opacity after development that _{effectively covers the remaining (} dye image-producing material associated with the SiI overhalide emulsion layers of the recording material. According to US Pat. No. 3,647,435, the opacity component of the Recording material can optionally be initially formed in situ, being incorporated between the image-receiving layer and the closest silver halide layer during the photographic development stage.

It is known from U.S. Patent 3,647,437 that the opacifying component contains a light absorbing substance such as a dye which acts as an absorbent at a first pH and which at the second pH into a substantially non-absorbent substance can be converted. According to U.S. Patents 3,473,925; 3,573,042 and 3,576,626 can use the opacifying and reflective components individually between

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see the sirber halide layer and the receiving layer through selective distribution from a tear-open container with several chambers. or from several tear-open containers to be built in. -

U.S. Patent 3,573,043 states that the polymeric neutralizing layer optionally between the dimensionally stable opaque layer and the closest essential one Layer, i.e. the closest layer of silver halide and dye image yielding Material may be incorporated around the ambient pH of the recording material to influence. According to U.S. Patent 3,576 • becomes a particulate acid in the recording material distributed to affect the ambient pH while after U.S. Patent 3,573,044 for solvent vapor of the developer solution permeable, dimensionally stable layers are used, around dye transfer by changing the solvent concentration to influence.

The recording material can also be constructed as it in U.S. Patents 3,594 to 64; 3 594 165i 3 689 262 and in the U.S. Patent Application Ser. Mo * 159,254. Thereafter -A photosensitive recording material contains a Transparent, dimensionally stable layer on which there is a receiving layer and one for the developer solution permeable opaque layer and a photosensitive Silver halide? Chscht. This record may also contain a separate dimensionally stable layer which is applied to the surface of the photosensitive Material can be placed opposite the dimensionally stable layer; furthermore, means such as a rupturable container can be used be provided with a developer solution between see the layer and the photosensitive section for Develop, can be distributed. From the relevant and The above-mentioned technical literature is also known that in Recording materials in which the recording section

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is immediately next to the transparent layer or the developer solution and / or the layer of the rest of the Recording material must be separated after the development stage, the latter layers possibly one may contain opacifying components.

Mach of US-PS 3,620,724 can said dimensionally stable The layer should be opaque or cloudy, in which case the light-sensitive silver halide layer is arranged directly adjacent to the opaque layer support and wherein the opacity component of the Developer solution permeable opaque layer of the Recording material in insufficient concentration is provided to prevent the passage of exposing actinic radiation, which, however, occurs after the development process possesses an opacity capability that effectively masks residual dye image-forming material associated with the silver halide layer remain. It is known from US Pat. No. 3,647,434 that the opacifying agent may optionally be present in the recording material can be formed in situ during the development stage.

U.S. Patent 3,188,209 states that the corresponding Sections of selectively sensitized silver halide and dye image-forming material of a recording material suitable for multichromatic diffusion transfer processes suitable, may have a construction in which the dye image-forming material in a silver halide-free Layer can be arranged, which is between two separate adjacent silver halide layers uniform spectral sensitivity can be located. Furthermore, a construction is given there, in which the dye image-forming material in a selectively sensitiv-. sized silver halide layer together with a separate, adjacent silver halide layer of the same spectral

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sensitivity is arranged and directly on the ' Layer carrier of the recording material is located.

The present invention is novel and. improved recording material for the diffusion transfer process, which is preferably produced as a uniform negative / Positive material (single sheet material) is present and with the photographic color image reproductions as a result of exposure of the recording material can be caused by incident actinic radiation.

Basically, the recording material to be used for the purposes of the invention is preferably constructed like the recording materials described in US Pat. Nos. 3,415,644; 3,415,645; 3,415,646; 3,473,925; 3,573,042; 3,573,043 ; 3,573 044; 3 576 625; 3 576 526; 3 594 164; 3 594 165; 3 615.421 % 3 620 724Γ 3 647 434; 3 647 435; 3 647 437; 3 661 585; 3 672 890; 3 689 262; 2 983 606 and 3 345 163. '

In general, these multilayer recording materials contain, in the relative order, a dimensionally stable, preferably a layer impermeable to actinic rays, one or more composite photosensitive Sections having a first photosensitive silver halide layer which is a particulate dispersion of silver halide, preferably of silver iodobromide, contains iodochloride or godchlorobromide grains which have a have first mean particle size. Furthermore is a second silver halide layer with a second mean particle size provided for diffusion transfer processes suitable color formers are assigned, the first mean particle size exceeding those of the second mean particle size and the first silver halide. layer. a sensitivity to incident actinishe Has radiation that is greater than the

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the ability of the second silver halide layer; further is a Layer for receiving image-forming material deposited thereon as a result of point-by-point exposure of the silver halide layer can diffuse; a (transparent) dimensionally stable one that is permeable to incident actinic radiation Layer; Means of providing an opacifying agent between the silver halide layers and the image receiving layer can be built in; Means with which a developing solution is brought into contact with the photosensitive layer can be. In a particularly preferred embodiment, the developer solution has a first pH, the dye image-forming material suitable for the diffusion transfer process during the developing step is diffusible and means with which the pH of the recording material from the first pH to a second pH in which the dye image-forming material can be influenced after substantial dye transfer image formation is not diffusible.

According to a particularly preferred embodiment of the present In accordance with the invention, a recording material of the general structure described above can be used after exposure in the presence actinic rays are developed. It is produced in such a way that between the receiving layer and the The closest silver halide layer after exposure is an inorganic light-reflecting pigment dispersion is introduced which contains a reflective pigment and at least one optical filter substance, the pH is above the pKa of the optical filter substance and where at the pH, the paraffin image-forming material is during the development stage is diffusible as a result of the exposure of the silver halide and the filter substance is present in a concentration in the mixture, so that an effective barrier against the permeability of actinic Radiation trains. The opacifier and the developer solution can, for example, with the help of a tear-open container

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be installed, in which the opacifier with the Developer solution is located and which is rigidly attached transversely to a leading edge of the recording material in such a way that that after the application of a compressive force, its content between the image receiving layer and the closest one Distributed silver halide layer. ·

Fig. 1 is a perspective view of the invention Recording material. ■.

Figures 2, 4- and 6 are .schematic, enlarged cross-sections through the recording material of Fig. 1, along the section line 2-2. Fig. 2 explains the sequence of layers in the exposure state, Fig. 4 in the development state and FIG. 6 shows the final state.

Fig. 3 _r 5 and 7 are other sehematische enlarged cross sections "by the recording material according to Fig. 2,. 4 and 6 taken along section lines 3-3, 5-5 and 7-7 ·

Fig. 8 shows the characteristic curves of a multicolored Dye transfer image according to the invention, which are compared directly to a corresponding prior art multicolor dye transfer image and where in the corresponding curves details relating to the transfer dye density as a function of exposure of the recording materials are given. '

It has already been mentioned that the development! A process in photographic diffusion transfer positive dye reflection image can be obtained, namely as a direct function of actinic radiation which is incident on a recording material which is preferably constructed in such a way that it contains several successive layers, namely a dimensionally stable support which is preferably opaque to incident radiation; a photosensitive silver halide layer comprising a

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Dye image forming material is assigned, which is in the Developer solution at a certain first pH as a result the point-by-point exposure of the silver halide layer is diffusible; a layer constituting the dye image Material which diffuses onto it, can absorb; a dimensionally stable, permeable to incident radiation Support; Means with which between the SiI overhalide layer and the receiving layer an opacifier, preferably an inorganic reflective pigment dispersion can be incorporated, the at least one optical filter substance or a dye in a sufficient Contains concentration, so that after the selective exposure of the silver halide layer, the silver halide layer can be protected from further exposure to actinic radiation, which affects the dimensionally stable Substrate is incident; Means by which the pH of the recording material can be changed from the first developing pH to a second pH at which the dye image forming material is essentially nondiffusible after substantial diffusion of dye image forming material Material has taken place on the recording layer.

It has now surprisingly been found that better photographic color reproduction is achieved by diffusion transfer development can be achieved if one has a diffusion transfer process ζ eic hämmmaterial use one or more composite photosensitive layers or groups of layers contains, which in turn is a first light-sensitive Layer with photosensitive silver halide, preferably Silver iodobromide, iodochloride or iodochlorobromide grains contains, which have a first mean particle size, and a second silver halide layer, which is preferably. has a second mean particle size, the first mean particle size is larger than the second mean particle size and the first silver halide layer is one for incident actinic rays are more sensitive to

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has as the second sirber halide layer and wherein the second sirber halide layer one for diffusion transfer processes Has dye image-forming material and a layer is provided which diffuses thereon Dye-image-forming material as a result of point-by-point exposure the photosensitive layer (s) 'can absorb by actinic radiation.

In a preferred embodiment of the present invention, the light-sensitive silver halide grains, preferably silver iodobromide, iodochloride and / or iodochlorobromide grains, which are contained in the first and second layers, have an average particle size distribution of about 0.2 to 3 » 0 ρ and preferably from about 0.5 to 2.0 ρ . ,

The use of diffusion transfer ink recording materials that contain the specified composite light * contain sensitive silver halide components per unit area coverage of the silver halide improved behavior in eiffusion transfer exposure the end; also by an increased exposure index for the diffusion transfer process as well as more efficient use of the silver that forms the dye image Components and the photographic auxiliary substances, e.g. from sensitizing dye components of the recording material.

Specifically, it has been found that the use of the composite photosensitive layers = improve the control of dye diffusion during the dye transfer process, which results in the image accuracy and the image resolution of the dye transfer image being made more favorable without the sensitometric properties being compromised. "transactions of the recording material are adversely affected ^·:...: ■■■ '.' ■:.. '■.

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In particular, it has been shown that particularly favorable results are obtained when, in contrast to a conventional light-sensitive silver halide and paraffin image-forming material containing this builds up roughly as follows: The color diffusion transfer recording material is constructed so that in the direction of exposure of the recording material a composite photosensitive section is built in, in which the initial exposure receiving photosensitive Silver halide layer is a highly sensitive silver halide dispersion comprised of relatively large grains but free of dye image forming material and radiation Absorbs wavelengths at which the emulsion is selectively sensitive and being immediately adjacent to the first photosensitive layer a second photosensitive layer with a relatively small grain size is provided, the Has dye image-forming material and due to their limited particle size and increased surface a high Has opacity. With such a layer sequence it is possible to achieve the high sensitivity of a light-sensitive Achieve large grain size silver halide in conjunction with optimal dye image control in one Transfer method that is obtained when a low-sensitivity photosensitive layer is used, the directly retains the material forming the dye image and which is necessary for optimal control of the dye · transfer, dye separation and dye image accuracy.

In preferred embodiments of the present invention the first and second photosensitive silver halide layers each contain a mixed halide of the above and the photosensitive silver halide will, usually with a total coverage of about 40 to

200 ing / 0.09 m, with the first photosensitive layer has a coverage of about 20 up to 100 mg / 0.09 m and the second photosensitive layer

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has a coverage of about 20 to 100 mg / square meter; eg 'is used in connection with a selected diffusion transfer process - color of the image-producing material and is present in a ratio of about 1 _f 5 to Qr ₉ A dye on light-sensitive silver halide, e.g. of about 30 up to 150 mg / 0.09 m dye to light-sensitive sirber halide, which is present in the above-mentioned coverage.

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The preferred photosensitive silver iodehlorbromid-, -iodochloride and -jödbromidschichten, which for the production used by photographic recording materials can be prepared by adding a water-soluble silver salt such as silver nitrate with at least one water-soluble halide such as ammonium, potassium or sodium chloride along with a corresponding one: iodide and bromide or an ammonium, potassium or sodium bromide together with a corresponding iodide, in an aqueous one Solution of a peptizer such as a colloidal gelatin solution. The dispersion is then digested at an elevated temperature in order to bring about increased crystal growth. The resulting dispersion is used to remove undesirable Washed reaction products and residual water-soluble salts, for example by using the preferred Gelatin matrix material applies and the dispersion cools, the settled dispersion noodles, the noodles with cold washing water washes or, alternatively, using one of the various flocculation systems or processes with which ■ can remove unwanted components, such as in DS-PS 2,614,928; 2,614,929; 2,728,662. To the after-ripening of the dispersion at elevated temperature together with the addition of gelatin or other polymeric substances, the desired and various auxiliaries, s.B. chemical sensitizers can be added, such as this in DS-PS 1 574 944; 1,623,499; 2,410,689; 2,597,856; 2,597,915; 2,487,850; 2,518,698; 2,521,926. All of this is done according to traditional methods, which C. B. Neblette in "Photography Its Materials and Processes", 6th edition 1962.

An optical sensitization of the silver halide crystals in the emulsion can be created by touching the emulsion with a effective concentration of the selected sensitizing dyes, dissolved in an appropriate dispersing agent such as methanol, ethanol, acetone, water and the like

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take place. All of this is done according to known methods, such as those used by FM, for example. Hammer in "The Cyanine Dyes and Related Compounds". - -

If necessary, further additives such as coating auxiliaries, hardeners, substances which affect the viscosity, stabilizers, protective agents and the like can also be added. They can also be incorporated into the emulsion by processes known per se for photographic emulsion production. '

The above-mentioned gelatin can be used as a binder for the corresponding emulsion layers in whole or in part by another natural and / or synthetic polymeric material that is permeable to the developer solution, such as albumin, casein or zein, or by resins such as cellulose derivatives (cf. US Pat. No. 2,322,085 and 2 541 474), can be replaced by vinyl polymers as they are known from the photographic literature. See US Pat. No. 2,945,771; 3,145,566} 3,142,567; Newman, "Comment on Non-Gelatin Film ;, BJOP, p. 434, September 15, 1961; and BE-PS 642 557 and 642 558.

In detail, a preferred silver iodobromide emulsion can be found easily made by using a single nozzle for 40 minutes and at one speed of 10 1 per minute at room temperature a solution of 3-molar silver nitrate in distilled water of a solution of 3-molar alkali halide (e.g. potassium) with a A bromide content of 98? S and an iodide content of 2 56 in one Trimellitic anhydride derivative with crude gelatine is added and the pH is previously increased with 5 μg sodium hydroxide 6 has set. The resulting silver iodobromide emulsion is then kept for the necessary time so that the relevant silver halide grain size distribution and separation of the derivative of silver 3odbromide with trimellitic anhydride and precipitated gelatin obtained by adding 2N sulfuric acid to the reaction mixture

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has been. The resulting precipitate is washed with chilled distilled water until the wash water is a Conductivity of about 300 to 500 u mhos / cm, then the volume with distilled water to 100 g lime-bone gelatin per 1000 ml of emulsion and then adjusted at about 56 ° C, a pH of 5 and a pAg of 9 Adding a sensitizing amount of a chemically sensitized solution containing 0.1 g of ammonium thiocyanate in 9 »9 ml Contains water and 1.2 ml of a solution, which in turn has 0.097 g of gold chloride in 9.9 ml of water and a '0.02 $ -ige aqueous sodium thiosulfate solution is present, bringing the mean Silver halide iodide crystal concentration supplied to an optimum will; the emulsion is then left to ripen for three hours at 60 ° C. and a pH of 5.5.

In preferred embodiments of the present invention, the composite photosensitive silver halide emulsions a diffusion transfer exposure index of more than about 50. This index gives the correct one Exposure value for a color diffusion transfer process to which an exposure meter, calibrated according to the ASA exposure index, must be adjusted to provide the correct exposure value for the formation of color transfer images made possible with satisfactory quality. The diffusion transfer exposure index is based on a characteristic H&D curve that corresponds to the original exposure ■ of the photosensitive silver halide emulsions to the corresponding Density curves is related, which form the resulting transmission image. Accordingly, the diffusion transfer exposure index is based on the exposure of the silver halide emulsions in a color diffusion transfer process must be exposed in order to obtain a usable color transfer image by this process. This value is sumjt directly as the exposure value on one Adjust camera to a suitable exposure of the recording material to achieve π.

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In accordance with the present invention, si.ch _r has also been shown that excellent diffusion transfer dye images can be obtained with a characteristic curve shape, that is, under control of the transmission image properties, which are graphically represented by the curve that an integral of the dye density of the transfer image as a function of the logarithm of the exposure value of the photosensitive silver halide layer. For this purpose, a photosensitive silver halide layer according to the present invention can be used, which has a first photosensitive silver halide layer with a mixture of differently photosensitive silver halide dispersions, of which at least one dispersion is the above-described silver iodochlorobromide, iodochloride and / or iodobromide -Dispersionen has in the ^r mixture, for example, with a second, and the same silver chlorobromide, -bromide- or preferably -iodobromide-, -iodochloride or -; iodochlorobromide dispersion (s), which has been prepared according to these approaches given here and where .The mixture preferably has an average particle size in the range given above from about 0.2 to 3.0 p. having. "

In detail, after mixing the above-mentioned takes different sensitive silver halide dispersions the characteristic curve of the dye transfer image, that results from using the mixture, the vertex shape, i.e. the exposure area of the low-sensitivity. Silver halide layer and there is a sensitivity i.e. a relative measurement that gives the reciprocal Represents exposure value that is required to achieve a given Achieve result, and from the most delicate Silver halide dispersion, while the toe portion of the reporting range of a sensitivity the least sensitive silver halide dispersion corresponds and thus increases the exposure area and thus the resulting flattening or the gamma value of the

Curve lowered. '*

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This opens up the possibility of controlled preparation of- photosensitive layers that cover a selectively broad range of predetermined gamma values or Contrasts and an "exposure behavior" or "dynamic" Areas ", that is, it is the relative dimension of the exposure area with which a useful Transfer dye image can be obtained. With the present invention, a high maximum density, a low minimum density and an extended dynamic range for the dye diffusion transfer system achieved so that there are dye transfer image differences, lighting differences on the one to be photographed Can reproduce the object better and more advantageously. For this one gets by with a minimal exposure time under optimal conditions and can reproduce the minimal differences, which are found in the shadow areas of the object to be reproduced, with the help of * some minimum density differences, in the resulting dye transfer 3 image.

In a preferred embodiment of the present invention consist the means by which the developer solution between the receiving layer and the closest silver halide layer is installed, from a tearable container in which there is a developer solution, whose Solvent concentration and pH meet the requirements. The tear-open container is rigidly arranged and extends transversely to a leading edge of the recording material, so that when the pressure is applied it releases the developer solution between the receiving layer and the next adjacent light-sensitive silver iodochlorobromide layer. In such an embodiment, the opacifying agent is preferably arranged in the developer solution, which is located in the tear-open container and then between the silver halide layers and the receiving layer after the selective exposure of the recording- materials is distributed.

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Multi-color images can be obtained by applying color images to the various components in the diffusion transfer method of the present invention. In one such approach, multicolor transfer images are obtained, for example using dye developers, using a unitary multilayer photosensitive material as described in U.S. Patent 3,415,644. Thereafter, at least two selectively sensitized photosensitive layers, which are superposed on a single support, are developed simultaneously and without separating a single conventional image-receiving layer. A suitable such arrangement comprises an "opaque support on which there is a red-sensitive silver halide layer group, a green-sensitive silver halide layer group and a blue-sensitive silver halide layer group, the silver halide layers or layer groups, for example a cyan dye developer, a purple dye developer and a yellow dye developer is assigned. At least one of the respective units contains a composite structure according to the invention and the dye developer to which this layer or layer group is assigned is located in the second silver halide layer of the respective layer group Dye developers can be arranged in their corresponding silver halide layers, for example in the form of particles, or they can be located as a layer behind the corresponding silver halide layer According to this publication, groups of layers and the dye developer assigned to them can optionally be separated from the other group by other suitable intermediate layers, for example by a layer of gelatin and polyvinyl alcohol. In certain cases it may be desirable to place a yellow filter in front of the green-sensitive emulsion, this yellow filter being inserted as an intermediate layer, if necessary

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however, if desired, a yellow dye developer can simply be used with the appropriate spectral properties serve as a yellow filter. In these cases a separate yellow filter can be used be dispensable. -

According to a preferred embodiment according to the invention contains a light-sensitive material suitable for the production of multicolored dye transfer images The following essential layers in the following order: The dimensionally stable, opaque layer support; at least two selectively sensitized silver halide layers or layer groups, each of which has one Dye image forming material assigned to a specific color e.g., dye developers of the type indicated above, which in the developer solution as a result of point-by-point exposure the correspondingly assigned filter halide layers are soluble and diffusible; a polymeric, from the dye image-forming materials, dyeable layer .; and one dimensionally stable transparent support and at least one selectively sensitized silver halide layer or layer group having a composite structure according to the present invention.

Because the preferred dye image-forming materials are dyes, the silver halide developing agents represent, for the sake of simplicity, the invention is further explained below with reference to such dyes, However, the invention should not be restricted thereto.

As mentioned above, the dye developers are 'compounds, which in the same molecule both the chromophoric system of a dye and a silver halide developer function contain. With the expression "silver halide developing function" denotes a group that can develop exposed silver halide. A preferred silver halide developer function is a hydroquinonyl group. Other

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suitable developer functions are ortho-dihydroxyphenyls as well as ortho- and. para-amino substituted hydroxyl groups. In general, the developer function includes a benzoid Developer function, i.e. an aromatic developer group that forms quinoid or quinone substances when oxidized.

The dye developers are preferably selected for their ability to form colors suitable for subtractive photography, that is, to give the above-mentioned cyan, purple and yellow colors. The dye developers used in each case can be incorporated into the corresponding silver halide emulsion or, in a preferred embodiment, in a separate layer behind the corresponding silver halide layer. In detail, the dye developer can be located, for example, in a coating or in a layer behind the corresponding silver halide layer. Such a dye developer 'winding layer can be distributed with a coating solution _r containing about 0.5 to 8 wt .- ^ of the corresponding dye developer in a film-forming natural or synthetic polymer, for example gelatin ^ polyvinyl alcohol and the like, so that this layer of the concerned diffusion transfer developing liquid can be penetrated.

' The silver layer groups contained in the light-sensitive multicolor laminate preferably show a predominant spectral sensitivity for separate areas of the

■ The spectrum and each layer or group of layers is assigned a dye which is a silver halide developer substance which is particularly preferably ₉ in the reduced form only essentially soluble at a first pH after development, but has a spectral absorption "range, which is essentially complementary to the predominant sensitivity range of the assigned emulsion . - ■ _. ■ _ ■■. ■ .. ■ _..-

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In the preferred embodiment, each layer is silver halide with the dye assigned to it in each case from the remaining layers with the dye assigned to it separated by separate polymeric intermediate layers permeable to alkaline solutions -

In one such preferred embodiment of the invention, more preferably, the silver halide layers comprise a first silver halide layer comprising photosensitive silver chlorobromide and / or iodobromide grains dispersed in gelatin, the layer being about 0.6 to 6 µm thick; a second silver halide layer with silver halide is also provided, the dye itself being dispersed in an aqueous alkaline solution of a polymeric binder, preferably gelatin. This layer is about 1 to 7 ρ thick; the polymeric intermediate layers which are permeable to alkaline solutions, preferably made of gelatin, are about 1 to 5 µm thick, the colorable polymer layer is transparent and about 6.55 to 10 * 2 µm. (0.25 to 0.4 mil) thick; The dimensionally stable, opaque and transparent substrates are impermeable to alkaline solutions, to those in the developer. Liquid vapors permeable and about 50.8 to Ί_52.4 p. (2 "Ms 6 mils) thick. It should be understood that the relative dimensions given above can be modified as appropriate to suit requirements.

Although in one embodiment of the present invention the dimensionally stable layers or support to be used have a vapor permeability rate of 1 or less grams / 24 hours / 6452 cm / 25 * 4 μ , in a preferred embodiment of the invention these layers have vapor permeability for the particular solvent of the developing solution: an average value of not less than 100 g / 24 stä. / 645 * 2 cm ² / 25.4 ii. In the case of the particularly preferred solvent, water, the steam

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permeability rate on average more than about 300 g water / 24 hours / 645.2 cm / 25.4 yes. "Here can it is advantageously a microporous polymer Act film with a pore distribution that does not affect the dimensional stability of the layers or, if necessary, also does not interfere with the optical properties of such layers. The pore distribution can, for example at an average pore diameter of less than about 20µ to greater than about 100µ and a pore volume from less than about 3, # to more than about 7 #.

In a particularly preferred embodiment of the present invention, the preferred solvent, water, can be used in a weight / weight ratio of about 1:10 to 1s25 dye: water with a ratio of about 1: 3 to 1:10 of liquid-permeable polymer to water will. It is particularly preferred to use about 300 to 1300 mg / 0.09 m of liquid-permeable polymeric binder, about 200 to 400 mg / 0.09 m of dye and about 5000 mg / 0.09 m ^{2 of} water. ■

The preferred dimensionally stable layers are designed in such a way that no liquid flow takes place through these layers while the vapor of the developer solvent can pass through by diffusion from the bulk of the evaporating liquid. The usefulness of the recording material is directly dependent on the nature and quality of the vapor-permeable membrane properties of the layers in question. the rate at which the required amount of developing solvent is withdrawn from the recording material after substantial dye transfer image formation by diffusion has occurred is consistent with maintaining the liquid impermeability and dimensional stability of the layers. So this should

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Layers have a maximum vapor permeability that allows the penetration of developer solvent and the allows dissolved gas at its vapor pressure without liquid from the developer solution can pass through. the Layers to be used in accordance with the present invention should therefore because of their solvent vapor permeability be as thin as possible, but have sufficient strength to withstand a chemical or to be able to withstand physical degradation of the recording material during its use.

In the preferred embodiment of the invention The corresponding silver halide / dye developer units are located on the recording material for the production of a multicolor transfer image of the photosensitive. borrowed section in the form of a tripack, which is usually a blue-green dye developer / red-sensitive Emulsion unit immediately adjacent to the dimensionally stable opaque layer, while the yellow Dye developer / blue-sensitive emulsion unit itself at the greatest distance from the opaque layer and the purple dye developer / green sensitive emulsion unit is placed between these units is. It should be noted that the relative order of these layers or units according to the respective requirements can be changed.

Referring now to Figures 1 through 7 of the drawings, a typical recording material in accordance with the invention is shown, wherein the same reference numerals refer to the same components.

As already mentioned, Fig. 1 shows a perspective View of a recording material 10. FIGS. 2 to 7 show schematic cross sections of the recording material along section lines 2-2, 3-3, 5-5 and 7-7 during various stages in the practice of the diffusion transfer photographic process.

4 0 9-824 / 103 1

The recording material 10 contains a tearable one Container 11, in which an aqueous Developer solution 12 is located. The photosensitive laminate 13 is made up of the following layers in the order given: A dimensionally stable, opaque one Support 14, preferably one for actinic rays impermeable flexible sheet material; a red-sensitive silver halide layer 15 with a blue-green developer dye; a red-sensitive one Silver iodochlorobromide, - ^ - iodochloride and / or iodobromide emulsion layer 16 with the properties mentioned above; an intermediate layer 17; a green-sensitive silver halide layer 18 with the purple dye developer; a green-sensitive silver iodehlorbromid-, -jadchlorid- ■ and / or iodobromide emulsion layer 19 having those described above Properties; an intermediate layer 20; a blue-sensitive silver halide layer 21 with the yellow ; Dye developer; a blue-sensitive silver iodochlorine, bromide, iodochloride and / or ^ odbromid ^ emulsion layer with the properties described above} an auxiliary layer 23, which may contain a silver halide donor auxiliary substance; an image receiving layer 24; a spacer layer 25; a new ' neutralizing layer 26 and a dimensionally stable transparent layer 27, preferably one for actinic rays permeable flexible sheet material.

. The structural cohesion of the laminate 13 is at least achieved in part by the adhesive force that exists between the; different layers of the laminate to the opposing ones Surfaces. However, the adhesive strength should at the intermediate surfaces between the image receiving layer 24 and the closest SilberjoÄchlorbrömid-j, -iodochloride- and / or iodobromide emulsion layer, for example the Adhesive force between the image receiving layer 24 and the auxiliary : layer 23 (see. Fig. 2 to 7) may be less · than it at the Intermediate surface occurs between the opposite Surfaces of the remaining layers forming the laminate,

A098 24/1 031

to the distribution of the developer solution 12 between the specified Image receiving layer 24 and the silver iodochlorobromide, iodochloride and / or silver iodochlorobromide lying next to it -Iodobromide emulsion layer to facilitate. The structural cohesion of the laminate can also be wholly or partially are reinforced or created by a connecting link, which extends, for example, around the edges of the laminate 13, the layers of the laminate, excluding the interface between layers 23 and 24 during the distribution of developer solution 12 between holds these layers together. As can be seen from the figures, the "connecting link" can be a act pressure sensitive tape 28 that secures the layers of laminate 13 at their edges and / or holds them together. The belt 28 also serves to hold the developer solution between the image receiving layer 24 and the next adjacent silver iodochlorobromide, iododehlorid- and / or iodobromide emulsion layer to hold after a compressive force has been applied to the container 11 and its contents between has distributed the specified shifts. Under these Under certain circumstances, the connecting belt 28 also prevents developer liquid from escaping from the recording material during and after the photographic development.

The tearable container 11 can be one of the usual embodiments act as they are for example in U.S. Patent 2,543,181; 2,634,886; 3,653,732; 2 723 051J 3,056,492; 3,056,491; 3,152,515 and the like are described. In general, such containers are rectangular Section made of liquid and air impermeable Sheet material that has to be sieved lengthways, even under Formation of two walls 29 is folded against each other along their longitudinal and end edges to form one Cavity are sealed, int which the developer solution 12 is located. The longitudinal edge seal 30 is weaker formed as the end edge 31, so that the former

■ 40-9824 / 1031

236.094 A

r .

can be broken open by hydraulic pressure, which is generated within the liquid 12 of the container when a compressive force is exerted on the walls 29 of the container is applied. ■ · ■

As in the Pig. 1, 2 and 3 is the container. 11 s ~ rigidly arranged and extends transversely to a leading edge of the photosensitive laminate 13 », whereby an emptying of the container contents 12 in a direction between the image receiving layer 24 and the indicated closest Layer after applying a compressive force to the Container 11 is reached. As can be seen from Fig. 2, extends the leading edge of the laminate ^ 13 so that its longitudinal edge closure 30 against the interface between the image receiving layer 24 and the auxiliary layer 23 directed is. It can be seen from FIGS. 1, 2 and 4 that the container 11 is rigidly attached to the laminate 13 with the extension 32 of the band 28 extending over a portion of the one wall of the container together with a separate retaining member as attached to the illustrated tape 33 which extends over a portion of the surface of the laminate 13, which generally occupies the same area as that covered by the tape 28

As can be seen from FIGS. 1, 2 and 4, the extension tab 32 of the belt 28 preferably have such an area and dimensions that for example after the manual severing of the container 11 and the tape 33 after distributing the desiccant 12 from the rest of the recording material 10, the flap 32 can be folded over the edge of the laminate 13, which was previously of the .Band 33 was covered in order to maintain the structural cohesion of the Laminate, for example, during unavoidable bends when storing and using the recording material rials to facilitate and order a suitable cover or to form a frame which allowed an image viewing area to be embedded on the transparent layer 27 through the the broadcast image can be viewed.

409824/1031

23609U

The container liquids are preferably an aqueous alkaline solution with a pH and a Solvent concentration at which the dye developers are soluble and diffusible. The container liquid also preferably contains an inorganic light reflective pigment and at least one optical filter substance at a pH above the pKa of this substance in a sufficient amount so that a Layer having an optical transmission density greater than about 6.0 and an optical reflection density less than about 1.0 and thus the exposure of photosensitive Silver emulsion layers 15, 16, 18, 19, 21 and 22 to prevent actinic radiation from occurring during the development through the dimensionally stable transparent support 27 in the presence of light is incident and by viewing directly the dye image formation in the image receiving layer during and after the formation of the dye transfer image to enable. As a result, the recording material may after the distribution of the developing solution in the presence of such. Rays are developed because of the silver halide or the emulsions of the laminate from incident radiation on one major surface through the opaque developer solution and on the other Main surface are protected by the dimensionally stable, opaque support. If the above mentioned Connecting tapes are also opaque, radiation can also penetrate the edges of the emulsion (s) be prevented.

The reflective pigment in question should be one which provides a suitable background for viewing the dye developer transfer image contained in the dyeable polymeric layer has been formed. Albeit generally used, essentially any reflection means it is preferable to use one that does not interfere with the color unity of the dye transfer image,

409824/1031

if it is "viewed and in particular a substance that is aesthetically" satisfactory for the viewer and does not form a disturbing background "or otherwise" adversely affects the information content of the image ", reflection means which give a white background for viewing the transmission image and in particular are particularly desirable those that are commonly used as backgrounds in reflection photography ₉ in particular substances that have the desired optical properties for the reflection of incident radiation «,

Examples of reflective pigments, which are suitable for the purposes of the invention are barium sulfate, titanium dioxide, barium like zinc sulfide _s silver flake, silicates ₉ alumina, zirconia, Zirkonacetylacetat, Ifatriumzirkonsulfat, kaolin, mica, and.

■ A particularly preferred reflection agent is titanium dioxide because of its high reflective properties. In general results in a preferred embodiment, based on titanium dioxide (weight / volume) with a developer solution about 1500 to 4000 mg / 0.19 m titanium dioxide, dispersed in

.100 ml of water, a percentage reflectance of about 85-90? S. In the particularly preferred embodiments: is percentage reflection on the order of more than about 85 ^.

In the embodiments in which the dispersion as preformed Layer between the receiving layer and the next adjacent silver iodochlorobromide, iodochloride »· and / or -iodobromide layer is arranged, is the pigment layer sufficiently transparent to allow exposure radiation to pass through the pigment layer; it can be called titanium dioxide Reflective means with a particle size distribution averaging less than about 0.2 ρ diameter and preferably less than about 0.05 ρ in diameter

409824/1031

have the state in which it is initially before the exposure of the recording material. Upon contact with the alkaline developing solution, this "preferred material will agglomerate into particles, preferably> than about 0.2 microns in diameter, and it will be present at a coverage of about 200 to 1000 mg / 0.09 microns. Specifically, the reflecting means in an insufficient amount is present to the exposure of the EMUI ~ sion layers to prevent actinic rays on the dimensionally stable transparent substrate of the recording material, but in a concentration sufficient after the development step the dye developer with the associated silver halide layers of the In a preferred embodiment, the pigment, such as titanium dioxide, is initially present in a relatively small particle size, surprisingly allowing radiation to pass through the reflective layer during exposure, while after contact with the al Kalischen developer solution and the agglomeration of the pigment particles an effective light reflection and a cover after the aggregation is achieved.

In general , those which can be used as reflection agents are those which remain essentially immobile within their developer batches during and after photographic development, and in particular those which form insoluble and non-diffusible inorganic pigment dispersions in the layer in which they are arranged.

If desired, reflectance pigments can accordingly be distributed in whole or in part in a polymeric matrix such as gelatin and / or any other polymeric matrix which is permeable to the developer solution, as it is in this. Description are given and are suitable as matrix binders. The reflective pigment can be distributed in one or more layers of the recording material ,

409824/1031

which lie separately or directly against one another can. This pigment can: also be located between the image • receiving and the closest adjacent Silberhaldgenidschicht are, provided that its distribution and Concentration is sufficient to ensure coverage after development. Finally, 'instead of of the above-mentioned measures or in addition to this, the reflection means can be arranged wholly or partially in the end of the developer solution residue between the image-receiving layer and the next adjacent silver halide layer with the dye image assigned to it Material be arranged.

The optical filter subsidence should be at a pH above their pKa their maximum spectral absorption for the irradiation at the wavelengths at which the light-sensitive silver halide layerCen) of the recording. materials are sensitive and they should essentially be inside the pigment dispersion while they perform their radiation filtering function unfolded, be essentially immobile or non-diffusible in order to use the optical unit of the dispersion as a radiation filter according to the present invention. to maintain and strengthen the spirit; this should their diffusion and local concentration within the image receiving layer can also be prevented, thereby reducing the Reduce the effectiveness of the reflective pigment dispersion as a background against which the image formation is immediate ■ during the initial stages of diffusion transfer development of the recording material can be viewed through the filter medium absorption of the dispersion, the visible Radiation reflects before the ambient pH falls below that The pKa of the filter medium has been reduced »In addition to the - spectral sensitivity range of the assigned silicon ■ over halide layer (s) can it be up to the "concerned, • Optical filter media around one or more filter dyes ■ act whose absorption is complementary to the silver halide is to provide effective protection against physical wear and tear

409824/103 1 · ■ /. .

tion that can arise from radiation during development. Taking into account that filter media absorption adversely affects image viewing due to contamination of the reflective pigment background, those substances should be selected which display their main spectral absorption at the pH at which the development is carried out, in order to have their minimum absorption at a pH below that which occurs during the formation of the transfer image. As a result, the optical filter media concerned should have a pKa below the developing pH and above the ambient pH after transfer image formation. The substances will preferably be selected which in a minimum concentration have an optical transmission density of> than about 6.0 at wavelengths at which the silver iodochlorobromide layer is maximally sensitive and an optical reflection density of < about 1.0 at these wavelengths.

Specific examples of such pH sensitive optical filter substances, useful for the purposes of the invention can be found in U.S. Patent 3,647,437, a publication which is expressly referred to here.

In general, preference is given to substances which have both an opacifying and filtering effect. These are those those within their environment during and after. photographic Development remain immobile and especially around insoluble and non-diffusible materials.

As we know from the relevant specialist literature, the Developer liquid for the development of multicolored Diffusion transfer images are generally an aqueous solution of an alkaline material such as diethylamine, Sodium hydroxide or sodium carbonate and the like. "Ti" -suggested it has a pH greater than

409824/1031

than 12 and contains in particular a viscosity-increasing one Compound that is a film-forming material that after distributing and drying the developer a re. relatively strong and stable PiIm. The preferred Film-forming materials are high molecular weight polymers, such as polymeric, water-soluble ethers, which are resistant to alkaline Solutions are inert, e.g. a hydroxyethyl cellulose or Sodium carboxymethyl cellulose. Film-forming people are also known Materials or thickeners whose ability to Increase viscosity, remains essentially unaffected, -if they are kept in solution for a long time. The film-forming material is preferably in the developing solution Contained in such amounts that it has a viscosity of more than 100 eps at about 24 ° C and preferably in the region of 100.0OQ cps to 200,000 at this temperature confers.

'During a diffusion transfer process for manufacture colored images with the aid of the recording material, this is exposed to rays that are sensitive to light Laminate aktini.sch. are and on the exposure surface of the laminate ", as illustrated in FIG. 3.

After exposure, the recording material (cf. Figures 2 and 4) by passing it through rollers 35 appropriately spaced opposite one another lets to exert a pressure on the tearable container 11, to tear it open at its longitudinal edge 30, and the alkaline Developer solution 12 »which is an inorganic, light-reflecting Pigment and an optical filter substance at a pH above the pKa of the filter substance and at a pH at which the cyan, purple and yellow dye developers as a result of the point-by-point exposure of the red-sensitive silver halide layers 15 and 16, the green-sensitive silver halide layers 18 and 19 and the blue-sensitive silver halide layers 21 and 22 or between the image receiving layer 24 and the auxiliary light 23 to be distributed.

409824/1 0 3 1

The alkaline developing solution 12 penetrates into the emulsion layers 15, 16, 18, 19, 21 and 22 in order to initiate the development of the latent images in the corresponding emulsions therein. The cyan, purple and yellow dye developers of layers 15, 18 and 21 are oxidized as a result of the development of their associated silver halide emulsions, preferably essentially as a result of their conversion from the reduced form to their relatively insoluble and nondiffusible form, to thereby produce imagewise distributions of mobile, soluble and non-diffusible blue-green, purple and yellow dye developer as a result of the point-by-point exposure of the corresponding emulsions. At least a portion of the imagewise distributions of mobile cyan, magenta and yellow dye developers are transferred by diffusion to the dyeable polymeric layer 24, resulting in a multicolored dye transfer image in that layer which can be viewed against the background formed by the reflective pigment ^1, which is located in the developer solution residue 12, which covers the blue-green, purple and yellow dye developers, the blue-sensitive emulsion layers 21 and 22, the green-sensitive emulsion layers 18 and 19 and the red-sensitive emulsion layers 15 and 16 remain assigned. After a substantial transfer image formation, a substantial portion of the ions of the aqueous alkaline developer solution 12 is transferred by diffusion through the permeable polymeric receiving layer 24, the permeable spacer layer 25 to the polymeric neutralizing layer 26, whereby the ambient pH of the system as a result of the neutralization to a pH drops, in which the blue-green, purple and yellow dye developers are essentially non-diffusible in their reduced form, thereby to give a stable multicolored dye transfer image and to free the pH-sensitive optical filter substance as a result of lowering the pH substantially below the pKa of this substance -

4 0 9 8 24/1031

set and thereby a maximum ability to reflect depending from the pigment concentration.

The alkaline solution component of the developer solution, the
between the. Photosensitive portion and the formation receiving portion is arranged, can thus penetrate into the emulsions to initiate the development of the latent images contained therein. The appropriately assigned dye developers are in unexposed areas as a result
the development of the latent images ". This mobilization is apparently at least partly due to a change in the solubility properties of the dye developers after oxidation, particularly with regard to their solubility in alkaline solutions.
This process can partly be traced back to a tanning effect on the emulsion due to oxidized developer substance and partly to a local exhaustion of alkali as a result of the development. In unexposed and partially exposed areas of the emulsions, the assigned dye developer is diffusible and thus produces an image-wise one
Distribution of non-oxidized dye developer, dissolved in the developer liquid, as a result of the point-by-point orientation of the corresponding silver halide emulsions.
At least a portion of this imagewise distribution of non-oxidized dye-developer is transferred to an overlying image-receiving layer during the development step, essentially excluding oxidized dye-developer. The image receiving section receives from the developed emulsion a diffusion of non-oxidized dye developer which varies in depth, without its image-wise distribution being significantly disturbed, and an inverted or positive one is obtained
Color image of the developed image.

409824/1031

-. 36 -

After the developer solution 12 has been distributed, the container 11 can be separated manually from the rest of the recording material to obtain the product shown in FIG. ■ -

The present invention is further developed together with the following

lowing information based on representative embodiments of the new photographic recording material according to the invention explained and described in detail. However, the following information is not intended to constitute a limitation.

For the production of a recording material as it is in Drawings shown is 127 "O ρ (5 mils) thicker opaque polyester backing coated one after the other with the following layers:

1 * One layer of the cyan dye developer

CH.

SO ₂ -NH-CH

HO

409824/1031

236O944

and red-sensitive silver iodine bromide having an average particle size of about 0.6 µm dispersed in gelatin; Coverage about 98 mg / 0.09 m ² dye, about 60 mg / 0.09 m ² silver, and about 92 mg / 0.09 m gelatin; >

2. a red-sensitive gelatin-silver iodobromide emulsion

an average silver halide particle size of about 1.4 µm;

2 2

Coverage about 60 mg / 0.09 m silver and about 27 mg / 0.09 m gelatin; _; ~. '.

3. a layer of butyl erylate / diacetone acrylamide / styrene / Methacrylic acid (60/30/4/6) and polyacrylamide in one ' ratio of about 29: 1; Coverage about 120 mg / 0.09 m;. .

4. a layer of the purple dye developer

HO-CH ₂ -

HO — CH ₂ -

-CH ₂ -CH ₂

OH

40 982A / 1031

-. 38 -

and of green-sensitive silver iodobromide a medium one. Particle size of about 0.6µ dispersed in gelatin;

ρ. - ρ

Coverage about 71 mg / 0.09 m of dye, about 35 mg / 0.09-m

Silver and about 50 mg / 0.09 m gelatin;

5 · a green sensitive gelatin silver iodobromide emulsion an average silver halide particle size of about 1.4 microns;

p p

Coverage, about 65 mg / 0.09 m silver and 40 mg / 0.09 m gelatin;

6. a layer containing butyl acrylate / diacetone acrylamide / styrene / methacrylic acid (60/30/4/6) and polyacrylamide in one

• ρ

Ratio of-about 29: 4; Coverage about 60 mg / O.09 m ϊ

7. a layer of the yellow dye developer

Aj-I-CH ₂ -

and the auxiliary developer 4 - methylphenylhydroquinone, dispersible

yelled in gelatin; Coverage - about 81 mg / 0.09 m dye,

ρ ο

about 15 mg / 0.09 m auxiliary developer and about 54 mg / 0.09 m Gelatin;

409824/1031

8. a blue-sensitive gelatin-silver iodobromide emulsion;

2 2

Coverage about 65 mg / 0.09 m silver and about 33 mg / 0.09 m Gelatine and -

9. a gelatin layer covering about 45 mg / 0.09 m. "

A clear, 127 µ (5 mil) thick polyethylene terephthalate support can be done sequentially with the following layers be coated: "- ■■ '■

1. Partial butyl ester of polyethylene / maleic anhydride mixed polymer; It was prepared by adding 300 g of highly viscous poly (ethylene / maleic anhydride), 140 g reflux n-butyl alcohol and 1 ml of 85 # phosphoric acid were heated. This became a polymeric acid layer with

2 produced a coverage of about 2000 mg / 0.09 m;

2nd time shift, containing a 60/30/4/6 copolymer in a 40: 1 ratio of butylacrylaf, diacetone acrylamide, styrene and Methacrylic acid and polyacrylamide in a coverage of about

500 mg / 0.09 m and ■

3. a 2: 1 mixture (parts by weight) of polyvinyl alcohol and

2 poly-4-vinylpyridine with a coverage of about 400 mg / 0.09 m, wherein a polymeric image receiving layer with the development retarder receives.

The two sections produced in this way can then be combined with one pressure-sensitive tape can be combined to form a laminate along their edges, with the tape in contact with the Sections extended around their edges

A tearable container with an outer layer of lead foil ' and an inner liner made of polyvinyl chloride contains an aqueous alkaline developer solution, for example, per 100 ml of water about 4.7 g KOH, about 0.8 g carboxymethyl cellulose, about 42 g TiO,

409824/1031

- ⁴⁰ - 23609U

about 1.3 g of N-benzyl-oC-picolinium bromide, about 2 g of one aqueous silica dispersion containing about 30 # SiOp and one or more antifoggants such as about 0.6 g Benzotriazole and about 0.03 g of 6-methyl-5-bromo-4-azabenzimidazole together with other auxiliary developer substances, e.g. those those described in U.S. patent application Ser.No. 246 669 of April 14, 1972 and which are readily available to the person skilled in the art are common. The container can then be rigidly secured to the leading edges of the two laminates with pressure sensitive tape be connected, which connects the corresponding container with the laminates, so that after the application of compressive forces onto a container by tearing open the side edge between the polymeric image-receiving layer and the closest gelatin layer.

The photosensitive composite recording materials can then be exposed to rays incident on the transparent polyester substrate and they are developed by drawing the exposed recording materials through suitable pressure-applying members are, for example, by rollers arranged opposite one another at a distance, as a result of which the container is torn open and its content is distributed. After the development step has been initiated, the formation of the multicolor dye transfer image may occur Viewed through the clear polyester backing against the titanium dioxide background be, which is due to the distribution of the pigment-containing developer solution between the layer 9 and the polymer Image receiving layer has formed.

Recording materials which have been produced according to the above information can be combined in the manner indicated with a comparative recording material of the same Layer sequence are exposed, but in the latter case no red-sensitive and green-sensitive silver iodobromide grains are contained in layers 1 and 4 and wherein the mean particle size of the licitsensitive

4 0 9 8 2 4/1 03 1 BATH

.23.6-0 SM

Silver iodobromide grains of layers 2 and 5, for example be about 1 u. The invention and the comparison on Drawing material is then exposed through a standard step wedge so that the characteristic Obtain curves of the corresponding dye transfer images which form the multicolored positive images (see FIG. 8). In detail, the characteristic Curves are obtained by looking at the density of the respective images in terms of red, green and blue Light as a function of the logarithmic exposure of the photosensitive Recording material, e.g. the characteristic curves of blue-green, purple and yellow Transfer image dyes (read according to red, green and blue-reflected light) of the invention and ver- same-recording materials.

From the characteristic curves given in the above This is obtained in a manner that is shown in FIG Recording material for a dye transfer process remove.

The gelatin-silver iodobromide emulsions can be as mentioned above prepared and spectrally sensitized in a suitable manner are dispersed by adding an effective amount of one or more optical sensitizing dyes in a suitable carrier solvent.

9824/1031

By adding an effective concentration of

2 36 09 A.4

COOH HOOC -

HOOC

The image formation of the developer solution can be observed immediately after the developer solution has been distributed, because in this way the photosensitive silver halide emulsion layers are protected from incident radiation due to the optical transmission density of the developer solution, which is more than about 6.0 density units. The image can be viewed against the reflective titanium dioxide background because the developing solution has a reflection optical density of - than about 1.0 density units.

4 0 9.824 / 10 3.1.

- ⁴³ ~. 23S0.9U

The pH and the concentration of the initially used alkaline developer solution are important a pH above the pKa of the optical filter components, "if the latter are used. This means that the pH at which about 50% of the substances in the less absorbent Form and about $ 50 in the more absorbent form are present, preferably a pKa of more than about and in particular of more than about 12 and corresponds to a pH, in which the dye developer used soluble borrowed and are diffusible. Although the specific pH to be maintained has been shown to be easy for each dye developer and any optical filter substance or for each group of dye developers and filter substances can easily be determined empirically, it is special it is desirable that the dye developers operate at pH are soluble above 9 and are relatively insoluble in reduced form at pH below, so that the system easily compensated for such dye developers, can. In addition, as mentioned above, the developer in the preferred embodiment one or more film-forming, Contain viscosity-increasing agents to facilitate the distribution of the developer and the distributed Developer as a structurally stable layer of the laminate to receive after distribution. However, it is not necessary that such a means as a component of the developer is used.

Neutralizing substances, e.g. a polymeric acid layer of the type described above are used in the erfindungsgeraässer Recording material incorporated to reduce the alkalinity of the developer solution from a pH above the pKa of the optical filter substance at which the dyes are soluble to a pH below the pKa of the substance at which the dyes are essentially • are not diffusible, in order to thereby further advantageously stabilize the reflection of the dye subextractive image

4 0 9824 / tu 3T

bilize and optimize it. In such a Pall, the neutralizing layer may contain a particulate, acidic reacting substance which is present in the Recording material or in a polymeric acid layer is arranged, e.g. as a polymeric acid layer approximately 7 »6 to 38.1 u (0.3 to 1.5 mil) thick between the transparent support and the image receiving layer and / or between the opaque Layer base and the closest group of emulsion layer and color former is located. The recording material may also be a polymeric spacer or barrier layer e.g. 2.5 to 17.8 µm (0.1 to 0.7 mil) thick, immediately adjacent to the nearest polymer Acid layer, located opposite the corresponding layer support, as mentioned above ..

In detail, a polymeric Acid layer be present, as it "for example in U.S. Patent 3,362,819. An inert time or spacing layer between the is also particularly preferred polymeric acid layer present on a support and the image-receiving layer.

As indicated in the last-mentioned patent specification, the polymeric acid layer can be polymers, which contain acid groups, e.g. carboxylic and sulfonic acid groups, those with alkali metals such as sodium, potassium and the like or with organic bases, especially with quaternary ones Ammonium bases such as tetramethylammonium hydroxide can form salts or groups that can potentially form acid contain, such as anhydrides or lactones, or other groups that can react with bases - by trapping them and hold back. The acidic reacting group is of course retained in the polymer layer. At the specified preferred embodiments contains the acid polymer free carboxylic acid groups and the transfer developer

A0Q824 / 1031

contains a high concentration of sodium and / or potassium ions. The acidic besonders'wirkungsvoll designated polymers are characterized in that they contain free carboxylic acid groups which are insoluble in the free acid form in water but water-soluble sodium and / or potassium salt form * - One can also polymers used _s the carboxylic anhydride contain, of which at least before the exposure period (development) have been converted into the free carboxylic acid groups. Although the most readily available polymeric acids are derivatives of cellulose or vinyl polymers, polymeric acids from other types of polymers can also be used *. provide examples of dibasic Polymersäuren.sind Säurehalbesterderivate of cellulose containing free carboxyl groups, z "Bo cellulose acetate hydrogen phthalate, Celluloseacetathydrogenglutarat, cellulose acetate hy drogensuccinat, Äthylcellulosehydrogensuccinat, Äthylcelluloseacetat-hydrogensuecinats Cellulpseacetathydrogensuccinat-hydrogenphthalatj ether and Esterderivate Cellulosej of which have been modified with Sulfoanhydriden, zobo with orthö -Sulfobenzoic anhydride, polystyrene sulfonic acid, carboxymethyl cellulose, polytrinyl hydrogen phthalate, polyvinyl acetate hydrogen phthalate, polyacrylic acid, acetals of polyvinyl alcohol with carboxy- or sulfo-substituted aldehydes, for example o-, m- or p-benzaldehyde sulfonic acid'or -carboxylic acid; partial esters of amy le n / maleic anhydride copolymers; partial esters of methyl vinyl ether / maleic anhydride copolymers; and the like.

As mentioned earlier, the pH of the developer should be preferred at at least 12-14 and the pKa of the selected optical filter substances are preferably in the region of 13 or higher. From the polymeric acid layer is stated that. it should contain at least enough acid groups that it reduces the pH from about 12 to 14 to at least 11 or lower after development and preferably to a pH of about 5 to 8 within a short time

409824/1031

Duration after development causes. This of course requires that the action of the polymeric acid be precisely controlled so that it does not interfere with either the development of the negative or the image transfer of the unoxidized dye developer. For this reason, the pH of the image layer must be kept at a transfer-functional value, for example 12-14, until the dye image has been produced, whereupon the pH is very quickly reduced to a pH below that at which the Dye transfer has occurred, for example to at least about 11 and preferably to about 9 to 10. Unoxidized dye developers containing hydroquinonyl developing groups diffuse from the negative to the positive as the sodium or other alkali salt. The rate of diffusion of such dye-image-forming components is at least in part a puncture of the alkali concentration and it is necessary that the pH of the image layer be maintained, for example, in the region of 12 to 14 until the necessary amount of dye has been transferred. The subsequent pH Erniedr · FINISH met addition to the desired effect on the light stability of the image, the valuable photographic function _s by suppresses substantially more dye transfer "

In order to avoid a too early pH decrease during transfer development, which for example would lead to an undesirable decrease in the density of the positive image, it is stated in the technical literature that the acid groups should be distributed in the polymeric layer in such a way that the speed with at which they are available for the alkali can be controlled, for example as a function of the swelling rate of the polymer layer _r a rate which in turn is directly related to the diffusion rate of the alkali ions. The desired distribution of the. Acid groups in the polymer layer can be achieved by mixing the acid polymer with a polymer free of acid groups or with a polymer which

409824/1031

has a lower concentration of acid groups and is compatible therewith, or by using only one acid polymer, but selecting one which has a relatively low proportion of acid groups. These embodiments are explained in the specialist literature by (a) a mixture of cellulose acetate and cellulose acetate hydrogen chloride and (la) a cellulose acetate hydrogen pyrchalate polymer with. a much lower percentage of phthalic groups than the first-mentioned cellulose acetate formate.

It is also stated that the layer containing the polymer Contains acid, a water-insoluble polymer, preferably may contain a cellulose ester to control or is used to modulate the speed at which the Alkali salt of the polymer acid "forms. Examples of cellulose esters, which are suitable for this are cellulose acetate, cellulose acetate butyrate and the same. The particular polymers and polymer combinations to be used become natural selected so that they have a "usable wet and dry" and, if necessary or desired, intermediate coats can also be used to ensure that the -different polymer layers better together while the storage and its application.

The inert spacing feature in the last-mentioned patent specification, e.g. an inert spacer layer containing polyvinyl alcohol or gelatin acts as a timing controller for the pH reduction of the polymeric acid layer. This timing is assumed to be a puncture of speed, with which the alkali passes through the inert spacer layer diffused. It is said there that the pH does not drop until the alkali has migrated through the spacer layer, d.ho the pH is only to no significant extent reduced by diffusion into the intermediate layer, but rather

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the pH drops quite quickly as soon as the alkali has passed through the Spacer layer is diffused ~.

In the above-mentioned ÜS-PS 3 362 819 it is stated that The presence of an inert spacer layer has been found to be effective in reducing the various reaction rates to adjust to each other over a wide temperature range, e.g. by preventing a too early pH decrease, if the development step is carried out at temperatures above room temperature, e.g. at 35-38 ° C (95-100 ° F) If an inert spacer layer is provided according to this publication, the speed, with which alkali becomes available for trapping in the polymeric acid layer, a function of alkali diffusion rates.

Now, however, according to US Pat. No. 3,455,686, the above should preferably be used mentioned rate at which the cations of the alkaline developer liquid, i.e. the alkali ions, are trapped available in the polymeric acid layer decrease with increasing transfer development temperature Dye diffusion transfer processes can be obtained over a wider range of relative ambient temperatures is independent of fluctuations in the positive transmission biia.

In detail it is indicated there that the diffusion rate of alkali through a permeable inert polymeric spacer layer with increasing development temperatures so increases significantly that, for example, at relatively high transfer development temperatures, e.g., above about 27 ° C (80 ° P) there is an early drop in transfer developer pH, at least in part because of the rapid diffusion of alkali through the dye transfer environment and their subsequent neutralization after contact with the polymeric acid layer. this applies

409824/103 1

especially for alkali, which is an inert spacer layer wandered through whose permeability to alkali is optimal for the temperature range in which an optimal transfer development takes place. Conversely, at-temperatures below the optimal transmission development range e.g. at below about 4.5 ° C (40 ° F) the last-mentioned inert spacer layer is an effective one Diffusion barrier, which temporarily prevents the effective crossing of the inert separation layer by alkali, whose rate of diffusion has been slowed down by temperature. This leads to the high pH of the The transfer development environment is maintained for too long a period, which leads to the formation of transfer image spots facilitated and leads to a degradation of the color content of the positive transfer image.

The last-mentioned US Pat. No. 3,455,686 also states that that by replacing the inert spacer layer in the image receiving section with a spacer layer, the one having permeable polymeric layer whose permeability is inversely dependent on temperature, i.e. if one uses a polymeric film-forming material, the decreasing Has permeability to solubilized alkali, derived from cations such as alkali and quaternary ammonium ions deteriorate with increasing temperature of the positive transfer image can be avoided which results from the above-mentioned too long maintenance and / or too early pH reduction. . .

Examples of polymers that have a permeability to alkali that is inversely dependent on the temperature are: HydroxypropyIpοIyvinylalcohol, Polyvinylmethylether, Polyethylene oxide, Polyvinyloxazolidön, HydroXypropylmethy! Cellulose, Isqpro.py.! Cellulose -:, - partial acetals of polyvinyl alcohol such as partial polyvinyl butyral, partial polyvinyl formal, partial polyvinyl acetal, partial polyvinyl propional and the same,

4Ö9824 / 1Ö3T

The last-mentioned polyvinyl acetals are stated to have generally saturated aliphatic hydrocarbon chains of a molecular weight of at least 1000, preferably from about 1000 to 50,000; they have a degree of acetalization of from about 10 to 3Ό '#, 10 to 30 S, 20 to 80 fi and 1.0 -bis # 40, based on the theoretically present in the polymer of polyvinyl alcohol hydroxyl groups?; this also includes mixed acetals.

If desired, a blend of the polymers can be used e.g., a mixture of hydroxypropylmethyl cellulose and partial polyvinyl butyral.

The use of the inventive Recording materials for color diffusion transfer processes results in extremely stable color transfer images because at least in part the ambient pH and the Solvent concentration can be adjusted to values at which no dye transfer after a substantial Transmission image formation takes place. The stable dye transfer image is obtained regardless of the fact whether the recording material was selected as a uniform laminate

. during exposure, development, viewing and storage of the recording material. The multicolored transmission images can be transmitted via a

A wider temperature range can be obtained without affecting the maximum and minimum dye transfer image densities. The yellow, purple and blue-green dye saturation, the blue, green and red tones as well as the color separation and handling properties are excellent. -

The dimensionally stable supports can be common opaque or transparent, rigid or flexible materials with the desired liquid impermeability and vapor permeability, e.g.

4038 24/1031

polymeric films of both synthetic and natural origin. Particularly suitable materials are impermeable to aqueous alkaline solutions, flexible polymeric materials which are permeable to water vapor, such as vapor-permeable polymeric films, which are derived from ethylene glycol terephthalic acid, vinyl chloride polymers, polyvinyl acetate, polyamides, methyl and ethyl methacrylate, ethyl and ethyl acetate, cellulose derivatives such as cellulose triacetate , - - ^; ■ - butyrate, - acetate propionate; Or - acetate butyrate derived, furthermore papers which are impermeable to alkaline solutions and permeable to water vapor ■; crosslinked polyvinyl alcohol, regenerated cellulose and the like.

Examples of materials that can be used for the image receiving layer suitable are polymers which can be dyed from solutions such as nylon, e.g., N-methoxymethyl-polyhexamethylene adipamide; partially hydrolyzed polyvinyl acetate; Polyvinyl alcohol with or without plasticizers; Cellulose acetate with filler e.g., one half cellulose acetate and one half oleic acid; Gelatin and other similar materials. Preferred Materials are polyvinyl alcohol or gelatin that contain a dye mordant such as poly-4-vinyl pyridine (See U.S. Patent 3,148,061).

It should be noted that the developer liquid ^ also Entwicklerhilfs- or accelerator substances such as p-Methylaminophenöl, 2 ^ - Diaminophenol, p-benzylaminophenyl, hydroquinone, Toluhydroquinone, phenyl hydroquinone, 4 ^r -MethyIpheny hydroquinone and the like can contain!. It is also possible to use several developer auxiliary or accelerator substances such as a 5-pyrazolidone developer substance and a benzoid developer substance (cf. US Pat. No. 3,039,869). Examples of suitable combinations of developer auxiliary substances are i-phenyl-3-pyrazolidone in conjunction with p-benzylaminophenoi and 1-phenyl-3-pyrazolidone in conjunction with 2.5

Α0982Α / 103

23609U

chinone. Such auxiliary developer substances can be found in the Developer liquid can be used or they can from the beginning at least partially in one or more of the Silver halide emulsion layers, in the layers which Dye developers or color formers contain, in the intermediate layers, the coating layers and the image-receiving layer or in any other auxiliary layer or layers be incorporated into the film. It should be noted that at least a portion of the oxidized during development Dye developer as a result of a reaction, e.g. Energy transfer reaction with the oxidation product an oxidized auxiliary developer substance can be oxidized and rendered immobile, the latter developing substance is oxidized by the development of exposed silver halide. Such a reaction of oxidized developer substance with non-oxidized dye developer, the auxiliary developer would react further with regenerate the exposed silver halide.

Furthermore, development can be carried out in the presence of an onium compound, in particular a quaternary ammonium compound (see US Pat. No. 3,173,786).

It goes without saying that the relative amounts of Components of the diffusion transfer developer can be changed to suit individual needs. It is also within the scope of the invention to use other additives, To modify alkalis and the like, provided that that the pH of the developer initially corresponds to the required first pH and the solvent concentration.If desired, Retarders, accelerators and the like can also be contained in the developer. In the same way, the Concentration of various components over, .a wide Range may vary and, if desired, can be customizable

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Components in the light-sensitive layer before being borrowed in a separate permeable layer of the light sensitive material and / or the light sensitive Emulsion be arranged, ..'.- ■ ".

In all examples the! Percentages of the components are percentages by weight, unless otherwise noted.

For an extensive list of dye developers see particularly suitable for photographic diffusion transfer processes can be found in US Pat. No. 2,983,606 and in the United States See the publications cited there, in particular in Column 27 of the patent mentioned. Examples of other US patents dealing with special dye ^ · employing diffusion transfer photographic process developers include U.S. Patents 2,985,506; 2,992 1Q6j 3,047-386; 3,076,808; 3 Q76 820; 3,077,402; 3,126,280; 3,131,061; 3,134,762; 3,134-65j 3,135,604; 3,135 6Q5; 3,135,606; 3,135,734; 3,141,772; 3,142,565 and the like.

Outside? the usual methods for direct dispersion a particulate solid material in a polymeric or colloidal matrix such as ball milling and the like-j, the preparation of the developer dye dispersion also take place in such a way that the dye is in a suitable solvent or solvent mixture whereupon the resulting solution in the polymeric binder dissolves is distributed, then optionally • * th solvent or the solvents are removed, for example by evaporation if one or more particular solvents have a sufficiently low boiling point or you can use the solvent in question or the Wash out the solvent in question if it has a sufficiently high differential solubility in the washing medium like water ^ compared to the solubility of the remaining components. But you can also use the polymer Binaamittssl and the dye in a common solvent to solve"

"- - 409824 / 1-03i1 -:

"V ⁵ 2380344

For further details regarding the treatment of solvent distribution systems refer to the above described Type and for a more detailed description of the solvents commonly used to achieve a distribution of photographic, Color-producing substances in polymeric binders, especially for manufacturing of layers in photographic recording materials, can refer to U.S. Patents 2,269,158; 2,322,027; 2,304,939; 2,304,940; 2 801 171 and the like.

Although the invention is based on the use of dye developers, materials giving the preferred dye image has been described, it goes without saying that instead of the specified dye developers also other dye image-forming materials, i.e., others Color formers, instead of the preferred developer dyes can be used. For example, one can use dye images resulting materials (see, e.g., U.S. Patent 2,647,049;

2,661,293 ■; 2,698,244; 2,698,798; 2 802 735; 3 148 062j

3,227,550; 3,227,551; 3,227,552j 3,227,554; 3,243,294; 3,330,655; 3,347 67/1; 3,352,672; 3,364,022; 3 443 939?

3,443,940; 3,443,941; 3 443 943) for which one -sich uses color coupling methods and wherein at least partially one or more color developer substances and a or multiple color formers or couplers together to form a dye transfer image on an overlying one Image receiving layer react. Color diffusion transfer processes can also be used (cf. US Pat 2,774,668 and 3,087,817), in which an imagewise differential transfer of complete dyes with Mechanisms takes place, with a transfer color balance image forms on an immediately adjacent image receiving layer. Finally, one can also use image forming materials use that are wholly or partially initially insoluble or non-diffusible in the recording material

409824/1031

are and during development as direct or indirect Diffuse function of exposure. "- .." '-'.

Although the above description of the invention based on preferred photosensitive components has been given, wherein in the recording material at least two selectively, sensitized photosensitive layers can be used directly on top of one another and lying flat, in particular with the preferred tripack structure, in which a red-sensitive silver halide emulsion layer, a green-sensitive Silver halide emulsion layer and a blue-sensitive silver halide emulsion layer is contained, which each one blue-green dye developer, one purple Dye developer and a yellow dye developer assigned is, the photosensitive portion of the recording material can be at least two groups of selective sensitized very small photosensitive. Elements contained in the form of a photosensitive Grid are arranged, each of the very small photosensitive Elements such as a suitable dye developer in or behind its corresponding silver halide emulsion assigned. Generally.contains a suitable light-sensitive grid very small red-sensitive emulsion elements, very small green-sensitive ones Elements and very small blue-sensitive emulsion elements arranged side by side in the manner of a rasteis and to which a blue-green, purple and yellow dye developer are assigned in a corresponding manner.

The present invention also extends to the use of a black dye developer and to the Use of a mixture of dye developers containing a black-and-white transfer image, as well as on the use by dye developers of the three subtractive colors in a suitable mixture, in such amounts of the Dye developer that the colors complement each other to black.

. 409824/1031

-. 56 -

23603U

If in the description the term "positive image" ·. was used, it should not be interpreted in a restrictive manner because it is mainly used for the purpose of explaining the invention, namely that it is based on the image-bearing layer formed the reverse image in the positive-negative sense with respect to the image in the photosensitive Describes emulsion layers. As an example of a different meaning of the phrase "positive image" may like serve the photosensitive material which is exposed to actinic rays through a negative transparency has been. In this case, the latent image in the photosensitive emulsion layer is a positive and the dye image, that has been produced on the image carrier layer is a negative. The phrase "positive image" is supposed to also include such a "positive" or image that has been produced on the image carrier layer.

It can be seen that the direct exposure of the film and Subsequent development resulting transfer image is a geometrically inverted image of the photographed object is. So if you want to get a geometrically non-inverted transfer image, the exposure of the film should be be done by an optical system that inverts the image, such as a camera, in which an optical system for inverting of an image is included.

In addition to the layers explained in the description, the recording material (film) according to the invention can also have one or have several coatings or layers, which in turn have one or more additives such as plasticizers may contain. Furthermore, essential intermediate layers can be present, for example in order to improve the adhesion. Finally, one or more of the described Layers may be composed of two or more layers of the same or different components,

409824/1031

who are directly next to each other or separated from each other One can, for example, by two or more iieutraiizing or inert layers or the same, where one of them is between the layer init the biatigrüneh Dye-forming IComporierite and the dimensionally stable opaque substrate can be located.

Claims (7)

2380344 Claims M./Multilayered light-sensitive photographic recording material for the dye diffusion transfer process, in addition to the usual layers, at least two photosensitive layers or groups of layers comprising a particulate dispersion of photosensitive silver halide grains and wherein the photosensitive layers or layer groups contain a developer dye Color coupler or another color former known for diffusion transfer processes is assigned, and furthermore an image receiving section on which the dye image-forming components are deposited after and during exposure Can diffuse development, thereby g e k e η η draws, that the silver halide grains of the first light-sensitive silver halide layer have a first middle Have particle size and the silver halide grains of the second silver halide layer have a second mean particle size which is smaller than the first middle Particle size and that the first light-sensitive silver halide layer between the exposure surface of the recording material and the image receiving layer being disposed, said first photosensitive image halide layer has a greater sensitivity to incident actinic rays than the sensitivity of the second photosensitive silver halide layer. 409824/1031 ^{BAD OR! GINAL} 2. Recording material according to claim 1, characterized in that g e k e η'η, that the first and / or second photosensitive silver halide layer is particulate Dispersion of photosensitive Silberjodchlorbromi'd-, Contains silver iodochloride or • silver iodobromide grains and the mean particle size of the grains in the first photosensitive Silver halide dispersion is preferably in the range from about 0.2 to 3 »0 μ. 3. Recording material according to claim 1 or 2, characterized in that the developer dyes, color couplers or other known for diffusion transfer processes Color formers are present in the second photosensitive layer in a coverage of 20 to 100 mg / 0.09 m. . , 4. Recording material according to claim 1 to 3, characterized in that g e - ke ή η ζ e ic hn et that the first photosensitive Silver halide layer between the exposure surface of the recording material and the second photosensitive Silver halide layer is located, the second being photosensitive Silver halide layer a developer dye, a color coupler or other for diffusion transfer processes known color former is assigned, ' 5. Recording material according to claim 1 to 4, characterized in that it is the photosensitive silver . ■ - si ρ '' halide in a coverage of 40 to 200 mg / 0.09 m - and "; ^ 40982Λ / Τ031 - the dye developer, color coupler, or the other for diffusion transfer processes known color former in a ratio of 1.5: 0.4 color former: silver halide contains. 6. Recording material according to claim 1 to 5, characterized in that it is in the specified order contains the following layers: a dimensionally stable opaque support; at least two selectively sensitized silver halide layers or layer groups with a predominant spectral sensitivity for separate areas of the visible electromagnetic spectrum, wherein at least one of the SiI overhalide layers a first photosensitive silver halide layer having a particulate dispersion of photosensitive silver iodochlorobromide, iodochloride or - Contains iodobromide grains that have a first mean particle size have and wherein a second photosensitive silicon halide layer a particulate dispersion of photosensitive grains of silver iodochloride, iodobromide or iodochlorobromide having a second mean particle size which is smaller than the first mean Particle size and wherein the first photosensitive silver halide layer between the exposure surface of the recording material and the second silicon halide photosensitive layer is arranged, and has a sensitivity to incident radiation at wavelengths, 409824/1031 23-0344 for which she has been selectively sensitized and which is greater than the sensitivity of the second photosensitive Silver halide layer for this radiation at the same wavelengths and wherein in the second photosensitive silver halide layer a developing dye, coloring coupler or another color former known for diffusion transfer processes is arranged * which is soluble and diffusible in an alkaline developer solution at a first pH and after development has a spectral absorption range which is essentially complementary to the predominant sensitivity range of the associated emulsion layer; ''''' a polymeric layer which is permeable to alkaline solutions and can be dyed; . a polymeric acid effect with that of an essential one Formation of the dye transfer image on the dyeable Polymer layer the first pH of the alkaline developer solution in which the color formers are soluble and diffusible a second pH can be reduced at which the color formers are essentially non-diffusible; · a dimensionally stable, transparent support and a tearable container with an alkaline developer solution a first pH and an opacifier in one sufficient amount to remove the color formers which selectively sensitized the Silver halide ^ emulsion layers are assigned to cover, with the tearable container with its Longitudinal edge is attached to the recording material that under the action of pressure his content in a 409824/1031 - ⁶² ~ 236Ö944 Direction between the dyeable polymer layer and the next adjacent selectively sensitized silver halide emulsion layer distributed. 7. Recording material according to claim. 1 to 6, characterized in that there is a red-sensitive silver halide layer with a cyan dye assigned to it, a green-sensitive silver halide emulsion layer with a magenta dye assigned to it and a blue-sensitive silver halide emulsion layer with a their assigned yellow dye contains at least one of the red-, green- and blue-sensitive silver halide emulsion layers a first and a second photosensitive silver halide bar, each of which contains one particulate dispersion of photosensitive silver iodochlorobromide, - ^ contains odehlorid or iodobromide grains, wherein the dispersion of the first photosensitive silver halide layer has a medium particle size, which is larger than the mean particle size of the dispersion the second photosensitive silver halide layer and with the first photosensitive silver halide layer therebetween the exposure surface of the recording material and the second light-sensitive silver halide layer is and greater sensitivity to incident Radiation at wavelengths to which it is sensitive than the sensitivity of the second light-sensitive Silver halide layer against radiation of the same wavelength. 409824/1031