DE2441751A1 - COMPOSITE FILM UNIT FOR THE PHOTOGRAPHIC DIFFUSION TRANSFER PROCESS - Google Patents

Description

October 24, 1974

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intie.oir. j. Ί el. 24 0275

Polaroid Corporation, Cambridge, Mass., USA

Composite film unit for photographic diffusion

transmission method

The invention relates to photographic film units for the color photographic diffusion transfer process in which a dye transfer image is formed point by point as a function of the respective degree of exposure by the diffusion transfer process. General state of the art

US Pat. No. 3,672,890 describes a composite photosensitive structure which is particularly suitable for use in color photographic diffusion transfer processes of the reflection type and which comprises, in the order given, the following essential layers: a dimensionally stable layer which is preferably opaque to incident radiation; one or more silver halide emulsion layers each having associated therewith a material suitable for dye image formation by the diffusion transfer process; a polymer layer which, in dissolved form, receives its diffusing dye-image-forming material; as well as a dimensionally stable transparent layer; the. Film unit can be exposed to incident actinic radiation and processed for development by placing between the silver halide emulsion layer and the image receiving layer a processing composition and an opacifying agent which can reflect incident radiation

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in an amount sufficient to make the silver halide emulsion to mask or cover assigned dye image-generating material.

According to a preferred embodiment of the patent mentioned For example, this composite photosensitive assembly comprises a rupturable container containing an alkaline processing composition and contains the opacifying agent and is fixed along a leading edge of the composite Structure is arranged so that when compressive pressure is applied to the container, the treatment composition between the facing surfaces of the image receiving layer and the next adjacent silver halide emulsion is emptied.

The liquid processing composition dispersed between the image-receiving layer and the silver halide emulsion penetrates the silver halide emulsion layers of the composite photosensitive structure and triggers the development of the latent images caused by exposure in the emulsion layers. As a result of this development of the latent images, the den. image-forming dye material associated with individual respective silver halide emulsion layers individually mobilized depending on the point-wise degree of exposure of the respective silver halide emulsion layers; this results in imagewise distributions of mobile dye imaging materials which can be diffused into the receiving layer to give the desired transfer dye image. Means are also associated with the composite structure which, after the essential dye image has been formed in the image receiving layer. film unit pH from a first processing or development pH at which the dye image forming material is diffusible as a function of exposure of the film unit to a second

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pH changes at which the transfer dye image has a shows increased stability; preferably a sufficient portion of the ions become an alkaline treating composition transferred by diffusion to a polymeric neutralization layer, reducing the alkalinity of the composite film unit from an initial alkaline treatment pH the second pH at which the dye imaging material is essentially nondiffusible thus substantially preventing further transfer of dye imaging material.

The transfer dye image is - as a reflection image through the dimensionally stable transparent layer is viewed against the background, which is caused by the opacification or Opacifier is formed as part of the treatment composition between the image receiving layer and the next adjacent silver halide emulsion layer was spread. The clouding or opacifying layer thus formed shields or masks the remaining imaging agent associated with the silver halide emulsion layer Dye material effectively after the development treatment.

In US Pat. No. 3,415,644 it is stated that the or dimensionally stable layer of the film unit next to the light-sensitive layer (s) is opaque, that the opacifying or opacifying agent is initially provided in an aqueous alkaline treatment composition and that the means for changing the pH of the film unit is between the transparent dimensionally stable layer and a polymer layer disposed on the image receiving layer which after the dye transfer image substantially is generated, the pH of an aqueous alkaline treatment composition from a first treatment or development pH, at which the dye or dye image-forming

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Material or ^ .. materials soluble and in composition are diffusible as a function of the exposure of the associated photosensitive silver halide layer, reduced to a second pH at which the dye image-forming material or materials in the are essentially non-diffusible. U.S. Patent 3,415,646 indicates that the photosensitive Silver halide layer or layers next adjacent dimensionally stable layer of the film unit for incident actinic radiation is transparent; U.S. Patent 3,415,645 further states that in one in such a case the opacifying agent from the beginning in the film unit between the image-receiving layer and the next adjacent silver halide layer can be arranged.

In U.S. Patents 3,615,421 and 3,661,585, it is stated that the opacifying and clouding component, respectively, of the Film unit optionally from the beginning as a pre-formed, for the treatment composition permeable layer between the image receiving layer and the next adjacent silver halide layer can be provided, namely in a concentration which, before the exposure, is insufficient for the passage of actinic exposure radiation to prevent, and which has such an opacifying or opacifying power after the development treatment, that effectively masks residual dye image-forming material remaining in the silver halide emulsion layers or is covered! according to US Pat. No. 3,647,435, the opacification or haze component of the film unit optionally at the beginning of the photographic processing of the film unit in situ between the image receiving layer and the next adjacent silver halide layer are generated.

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In US Pat. No. 3,647,437 it is described that the opacifying or clouding component can optionally comprise a light absorbing reagent such as a dye which is in an absorbent form at the first pH and in an absorbent form at the second pH can be converted to substantially non-absorbent form; according to the US Patents 3473925, 3 573 and 3,576,626 can send a Opazifierungs- or turbidity component and a Refle'x-ionskomponente separately be placed between the silver halide layer and the image receiving layer, by selective distribution of a composite rupturable container or more tear-open containers.

In US Patent 3,573,043 it is disclosed that the polymeric neutralizing layer optionally between the dimensionally stable opaque layer and the next adjacent substantially layer, that of the next adjacent silver halide / dye image forming component can be arranged to the predetermined change in the pH level in the To effect film unity. The US ^ Patent 3,576,625 describes the use of particulate in the Filmein integrated distributed acid to effect the modulation of the pH-level, and the US Patent 3,573,044 the use of reduction of the vapor of the solvent of the treatment composition dimensionally stable permeable Layers for process control of dye transfer as a function of solvent concentration.

If desired, the film unit can also be formed according to U.S. Patents 3,594,164, 3,594,165, 3,689,262 and 3,701,656 as a composite photosensitive structure having an image-receiving layer, one for the processing composition, on a transparent, dimensionally stable support

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a transparent opaque layer and a photosensitive silver halide layer, the film unit comprising a may comprise a separate dimensionally stable sheet that is on the opposite surface of the dimensionally stable layer of the photosensitive structure can be applied, as well as a device such as a tearable A container from which, for development treatment, a processing composition is sandwiched between the above-mentioned cover sheet and the photosensitive structure can be distributed. In some of the last-mentioned patents it is also described that in structures in which the light receiving part is arranged immediately adjacent to the transparent layer or the treatment composition and / or the sheet after the Development treatment 'is separated from the remainder of the film unit, the latter elements are optional may have an opacifying or opacifying component.

According to US Pat. No. 3,620,724, the dimensionally stable layer mentioned there can be opaque, in which case Trap the photosensitive silver halide layer next to the opaque support layer and the opacifying or opacifying component of the opaque which is permeable to the treatment composition Layer of the film unit in this is present in a concentration that is insufficient to allow the passage of to prevent actinic exposure radiation, which however, after the development treatment, causes an opacification or Haze, the rest in the silver halide layer Effectively covers residual color former; according to US Pat. No. 3,647,434, the opacification or opacifiers optionally in such a film unit in situ during the development treatment of the film

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unit can be formed.

According to British patent specification 874 046, at the same time two or more separate diffusion transfer images by exposure and diffusion transfer treatment one Film unit obtained, which during the development treatment has a transfer image-receiving layer in the immediate Plant against one major surface of a silver halide emulsion layer as well as having an image receiving element in abutment against the opposite major surface "of the emulsion - and wherein after the development treatment, the image-receiving member separated from its covering with the emulsion and, if necessary, the emulsion also from its system against the image receiving layer is peeled off in order to be able to view the relevant transmission images.

General description of the invention

The invention relates thus generally a film unit for the color photographic diffusion transfer process and more particularly to a containing the negative and positive as integrals, one-piece, unitary film unit of this type to generate photographic Falbbilder according to the diffusion transfer process as a function of exposure of such a film unit with actinic radiation ^"s

The invention has for its object a further improvement such a pilm unit and the diffusion transfer image obtained with it in terms of the amount of dye image-forming materials required and more controlled Transmission diffusion is used to generate the transmission image.

For this purpose, a composite film unit for the diffusion transfer photographic process disclosed in

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a layer on a dimensionally stable support at least one light-sensitive silver halide layer which is used for dye image formation by the diffusion transfer process appropriate dye material (color former) assigned is, as well as a dyeable layer (image receiving layer) for receiving color former diffusing into this layer from the light-sensitive silver halide emulsion layer (s) (s) assigned color former layer (s), provided according to the invention that the film unit forming Layering on the side of the light-sensitive silver halide emulsion layer (s) opposite the dyeable image-receiving layer a development treatment composition used in the diffusion transfer process permeable, for the diffusion transfer dye image formation Serving dye material, however, has impermeable barrier layer.

Since the laminate forming the film unit according to the invention has a barrier layer which is permeable to the development treatment composition but not to the image-forming dye materials used, a penetration or extraction of developer dye dissolved in the processing composition from the photosensitive laminate into the treatment composition is due to the different dye concentration gradients between the Laminate and the site of the initial incorporation of the developing composition, thereby greatly reducing the effect of the processing compositions commonly used in dye diffusion transfer processes as dye sinks. By substantially restricting the diffusion of the dye during the processing of the film unit to the photosensitive laminate, an improved yield and more economical utilization is achieved by reducing the amount of dye required per unit of dye density of the transfer image; at the same time, this results in an optimal control of the dye through the associated silver halide

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Genid layer as a function of the point-wise extent of exposure the layer with actinic radiation, resulting in increased sharpness of the resulting dye transfer image.

According to the invention, the film unit has multiple layers in the order given: a first dimensionally stable layer which is transparent to actinic radiation; the one mentioned for that of diffusion transfer imaging serving dye material impermeable, however for the development treatment composition permeable barrier layer; one or more light-sensitive silver halide layers, to which one or more image-forming dye material (s) suitable for the diffusion transfer process ("color formers") assigned; an opaque opaque layer; a transparent layer for receiving what diffuses into it imaging dye material ("color former") and a second dimensionally stable layer permeable to incident actinic radiation; Means for generating or introducing a Opacifying or opacifying agent between the first dimensionally stable Layer and that for the dye imaging material impermeable barrier layer; as well as means for contacting a treatment ·.

composition with the photosensitive layers; as. ¹ -according to a particularly preferred embodiment, a treatment composition which has a first pH at which the image-forming dye material ("color former") of the diffusion transfer process is diffusible during the development treatment, and means for reversing the pH of the film unit from the first pH -Value to a second pH value at which the image-forming dye material ('· color former ¹¹¹ ) is essentially non-diffusible after the formation of the dye transfer image.

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According to a particularly preferred embodiment of the invention, which relates to a film unit of the general construction described above, which is made after taking exposure can be developed in the presence of actinic radiation. that as after the shooting exposure between

the first dimensionally stable not and the one for the imaging Dye material impermeable barrier layer to be introduced Opacifying agent an inorganic light reflective end Pigment dispersion is used; ais' device for introduction the opacifying agent and the treatment composition can serve as a tear-open container, which the opacifying or opacifying agent in the specific Contains treatment composition and along a leading edge dej? .Filmeinheit is fixedly arranged in such a way that it is at Exerting a compressive pressure its contents between the first dimensionally stable layer and that for the imaging dye material impermeable barrier layer distributed.

Detailed general description of the invention

The photographic diffusion transfer process is within the scope of the basic inventive concept set out above to achieve a dye-positive reflection image as a direct function of the auxiliary exposure in a special Wise constructed film unit used with actinic radiation; the film unit preferably has multiple layers in in the order given: a first dimensionally stable, radiation-permeable layer; a first for the treatment composition permeable but impermeable barrier layer to diffusing dye imaging material; one or more photosensitive silver halide substances, one or more dye-forming material (s) suitable for the diffusion transfer process "Color formers" are assigned; an * opaque, opaque layer;

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a second layer, which diffuses into it, take up imaging dye material ("color former") can; a second dimensionally stable layer permeable to incident radiation; a device by means of which between the first dimensionally stable layer and the next adjacent ones opaque to the dye imaging material Barrier layer an opacifying or opacifying agent can be introduced, which is preferably an inorganic reflective pigment dispersion

sion acts · in a concentration that after

selective uptake, exposure of the silver halide layer, the dimensionally stable layer striking actinic radiation ensures an effective protection of the silver halide against further exposure through _a uf; and means for changing the pH level of the film unit from the first or treatment pH to a second pH at which the dye imaging material ("color former") is essentially nondiffusible after the primary imaging diffusion into the image receiving layer is complete .

ORIGINAL IMSPECTEO

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Preferably, as image-forming dye materials, dyes which, as indicated above, are also silver halide developers are used for the sake of simplicity and clarity, the invention is described below on the basis of such dyes, but without this de invention is limited to the dyes named in the exemplary embodiments; accordingly is the invention Film unit with regard to its structural design below on the basis of the preferred embodiment mentioned above without the invention being limited to this particular structure.

The developer dyes are compounds that are in the same molecule, both the chromophore system of a Contain dye as well as a silver halide developer function. Under "silver halide developer function" is understood a group suitable for developing exposed silver halide. A preferred silver halide developing function is a hydroquinonyl group. Further suitable developer functions are the orthodihydroxyphenyl group as well as ortho- and para-amino-substituted hydroxyphenyl groups. In general, the developer function is benzoid Developer function, i.e. an aromatic developer group, which forms quinonoids or quinone substances when oxidized.

The developer dyes are preferably according to their Ability to form colors suitable for subtractive color photography, i.e. to form cyan, Magenta and yellow. The developer dyes can either, according to a preferred embodiment, in the relevant Be incorporated silver halide emulsion, or in a separate, adjacent to the silver halide layer in question Layer be provided. In particular, the developer dye for example in a coating or a layer

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behind or immediately in the relevant silver halide layer be arranged; such a developing dye layer can be applied using a coating solution which are about 0.5 to 8 wt .-% of the respective developer dye distributed in a film-forming natural or synthetic polymer such as gelatin, Polyvinyl alcohol or the like, that of each treatment composition used as a diffusion transfer medium can be penetrated.

A comprehensive compilation of specific, especially for Use in diffusion transfer photographic processes suitable developer dyes are disclosed in U.S. Patent 2 9 83 606 and the other US applications mentioned therein, in particular those in the table in column 27 U.S. applications listed in U.S. Patent 2,983,606. · As examples of other US patents in which specific Developing dyes for use in photographic Transmission processes are dealt with in detail, the following US patents 2,983,605 are listed,

2 992 106, 3 047 386, = 076 808, 3 076 820, 3 077 402,

3 126 280, 3 131 061, 3Ί34 762, 3 "134 765, 3 135 604,

3 135 605, 3 135 606, 3 135 734, 3 141 722, 3 142 565 and " Further.

The individual silver halide layers or layers, which forming the photosensitive multicolor laminate, preferably have a predominant spectral sensitivity for mutually different areas of the spectrum / and each such a silver halide layer is assigned a developer dye, which is preferably essentially in the reduced form is only soluble at a first pH value and after the development treatment a spectral absorption

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possesses area that is essentially complementary to the the main sensitivity range of the emulsion assigned to it.

Permitted according to a preferred embodiment of the invention the film unit specifically enables the formation of a multicolor dye transfer image, the photosensitive Laminate has in succession at least two selectively sensitized silver halide emulsion layers, the each is assigned an image-forming dye material of a given image color after the development treatment, that essentially only at a first pH value as a function of the uptake exposure of the silver halide emulsion layer assigned to it in each case is soluble and diffusible.

The silver halide emulsions constituting the multicolor photosensitive laminate preferably each have a predominant predominant spectral sensitivity for one another different areas of the spectrum, and each emulsion is assigned a dye, which is also a silver halide developer is and is preferably soluble in the reduced form only at a first pH and after Incorporation or development treatment has an absorption spectral range that is substantially complementary the main prevailing sensitivity range the emulsion that is ordered to it. In particular, dyes are preferred which - during the exposure of the emulsion - a main spectral absorption outside the primary spectral ranges for which the assigned silver halide emulsion is sensitive, and have a spectral transmittance substantially complementary to this absorption and the - after exposure or development treatment the emulsion - a main spectral absorption within the spectral range for which the assigned silver halide

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emulsion is sensitized and has a spectral transmittance substantially complementary to this absorption; Examples of such developer dyes are in U.S. Patent 3 307 947.

According to one embodiment of the invention, the individual Emulsion layers, and the dyes assigned to them, from the other emulsion layers and their assigned Dyes, each separated by separate polymer interlayers that are permeable to alkaline solution, and the dyeable polymer layer closest to the polymeric acid layer can pass through from the polymer acid layer a polymer spacer layer permeable to alkaline solution be separated, preferably by a polymer spacer layer, whose permeability to alkaline solutions decreases with increasing temperature.

According to preferred embodiments of the invention, there is the silver halide emulsion of photosensitive silver halide dispersed in gelatin and has a thickness from about 0.6 to 6 microns; the dye itself can be in a polymer binder permeable to aqueous alkaline solution, preferably gelatin, dispersed as a separate layer about 1 to 7 microns thick; those for alkaline Solution-permeable and dyeable polymer layers are transparent and can have a thickness of about 0.25 to 0.4-thousandths Own customs; the polymeric spacer layers - permeable to alkaline solution - are transparent and can be about 0.1 to 0.7 thousandths of an inch thick; the alkaline solution permeable polymeric acid layers are clear and can measure about 0.3 to 1.5 thousandths of an inch be fat; the dimensionally stable transparent layers are impermeable to alkaline solutions and can have a thickness

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from about 2 to 6 thousandths of an inch. Of course can have the relative dimensions given above

can be changed appropriately as required with regard to the particular desired product.

According to the preferred embodiment of the invention, which a film unit for the production of a multicolored transfer image the corresponding silver halide / dye developer units are located of the photosensitive member in the form of a tripack arrangement, which is usually a yellow dye developer / blue sensitive unit Emulsion, a cyan developer dye / red-sensitive unit Emulsion and a unit of magenta dye developer / green sensitivity liehe arranged between these two units Has emulsion, the relative succession of these units, of course, optionally modified can be.

In the cases where of the yellow dye developer and the Magenta developer dye, preferably in tripack configuration in which the yellow dye developer / blue sensitive emulsion unit removes of the opaque layer and the dimensionally stable clear layer and the unit-cyan developer dye / red-sensitive Emulsion are arranged next to the opaque layer to give the multicolored transfer image, so in cases where the yellow and the Magenta dye developer either or both are a dye developer that - during exposure of the emulsion to light main spectral absorption outside the primary spectral range for which the associated silver halide emulsion is sensitive, and a spectral transmittance substantially complementary to this absorption

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possesses, it can be advantageous in many circumstances to Incorporate filter substances to ensure the correct selective exposure of the emulsions located less close to the exposure surface of the laminate. In particular can * in a case where the yellow dye developer a major spectral transmission within the primary spectral range for which the associated silver halide emulsion sensitive, i.e. within the blue region of the visible spectrum, during exposure which has emulsions, a yellow filter substance can advantageously be used embedded between the blue sensitive emulsion and the remaining green and red sensitive emulsions are to avoid unwanted exposure of these last-mentioned emulsions due to their inherent sensitivity to actinic radiation in the generally present blue area of the spectrum in a case where the magenta developing agent used is a major one spectral transmission within the primary sensitivity range its associated silver halide emulsion, i.e. within the green region of the visible spectrum, Has during the exposure of the emulsions, a magenta filter substance between the green and red-sensitive emulsions can be incorporated, in cases where the Et-sensitive emulsion is at the same time sensitivity for actinic radiation in the green range of the visible Spectrum owns.

In the following, embodiments of the invention are based on the drawing described; in this. Tend:

1 shows a partial perspective view of a photographic one Film unit according to an embodiment of the invention,

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Fig. 2 ,. 4 and 6 are enlarged schematic sectional views, respectively of the film unit of Fig. 1, in section along line 2-2, for illustrative purposes the assignment of the individual elements during the three stages shown in the course of a diffusion transfer process for generating a multicolored transfer image according to the invention, namely during the exposure stage (Fig. 2), a development treatment stage (Fig. 4) and as the end product of the process (Fig. 6 ·), the thickness of the one of its layers of material is greatly exaggerated.

3, 5 and 7 are even more enlarged schematic sectional views of the film unit according to FIG. 4 and 6, each in section along the line 3-3, 5-5 and 7-7 to further illustrate the arrangement of the layers forming the photosensitive laminate during the three illustrated process stages the transfer process;

8 shows a perspective view of a film pack with several film units,

Fig. 9 is a longitudinal sectional view taken along line 9-9 in Fig. 8, i.e., substantially midway between the Side edges of the film pack from FIG. 8.

In the following now 'first with reference to Figures 1 to 7 a Film unit according to a preferred embodiment of the invention described, wherein the same reference numerals in the various drawing figures refer to the same Refer to parts.

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1 shows the film unit designated as a whole with 10 in a perspective view, FIGS. 2 to 7 respectively schematic sectional views of the film unit 10 along the Section lines 2-2, 3-3, 5-5 and 7-7, during the various stages shown in the course of one below diffusion transfer photographic process described in detail.

The film unit 10 has a tearable container 11, which contains an aqueous alkaline solution 12 before the development treatment; furthermore a light-sensitive one Element 13 comprising the following layers in the order given: a dimensionally stable clear one Layer 24a; a neutralization layer 23a?

V "

a marginal layer 22a; one for the handling together- '~. Settlement permeable, but for that which forms a dye image Impermeable barrier material 25; a blue-sensitive silver halide emulsion layer 15 which contains a yellow developer dye; an intermediate layer 16; a green-sensitive silver halide emulsion layer 17, containing a magenta developing dye; an intermediate layer 18; a red-sensitive silver halide emulsion layer 19 containing a cyan dye developer; an opaque one Layer 20, an image receiving layer 21b; a spacer layer 22b; a neutralization layer 23b; as a dimensionally stable transparent layer 24b; both Layers 24a and 24b consist of one that is transparent to actinic radiation but opaque to the treatment composition flexible sheet or foil material.

The photosensitive element 13 may be provided with a bezel 26 which extends around the edges of the indicated layers of the element and holds it together, except for the interface between the spacer layer 22a and the barrier layer 25 during the distribution of the treatment composition 12. Wi @ in der Shown in the drawing , the a *

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Version consist of a pressure-sensitive adhesive tape 26 which holds the individual components of the photosensitive element together at the indicated edges of the film unit 10. The adhesive tape 26 also acts to entrap the treatment composition 12 between the first spacer layer 22a and the barrier layer ■ 2 ^: j

after the application of a pressing pressure on the container 11 and the distribution of its contents between the mentioned layer components 22a and 25. Under these circumstances, the adhesive tape 26 prevents leakage of the treatment composition from the film unit during and after the photographic development processing.

As shown in the drawing, the binding sheet 26 overlapping and attached to the rear edge of the transparent cover layers 24a and 24b cooperates with the rear edge of these two transparent layers to form a closed chamber or trap 2 which can receive and contain excess treatment composition 12; the treatment composition 12 is applied in excess in order to ensure sufficient area coverage by the treatment composition when it is distributed. To further facilitate the distribution of the treatment composition 12 between the transparent layer 24a and the transparent layer 24b, the infaßband 2i y ocler several air outlet openings 1 can be provided in association with the rear edge of the film row and preferably in direct connection with the collecting chamber 2 in order to allow the air outlet from the film unit during the dispensing of the treating composition 12.

The rupturable container 11 is of the US-patents 2,543,181 in the _f 2,634,886, 2,653,732, 2,723,051, 3,056,491, 3,056,492, be shown and described kind 3,152,515. In general , these containers consist of a right

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BATH ORIGINAL

square piece of a T, such that two walls 2 7 are formed lüssigkeits- and air-impermeable sheet which is folded longitudinally on itself that are joined sealingly together along their long-side and end-face edges, and such a cavity or a chamber for the Form treatment liquid 12. The sealing connection along the longitudinal edge 28 is made with less strength than the end connections 29, in such a way that it is torn open by the hydraulic pressure which is generated in the liquid 12 of the container when a compressive pressure is exerted on the container walls 27.

As can be seen from FIGS. 1, 2 and 4, the container is fixedly arranged and extends across the front edge the photosensitive layer 13; In this way, when a compressive pressure is exerted on the container 11 a directed emptying of the container contents 12 between the first spacer hole 22a and the barrier layer 25 is ensured. As shown in Fig. 2, the container is fixed transversely along the front edge of the layer 13,

its longitudinal edge seal 28 towards the front surface
edge of the limit mentioned. As shown in Figs. 1, 2 and, the container 11 is attached to the bed 13 by means of an extension 30 of the enclosure 26 which extends over a portion of a wall 27 of the container in connection with a separate hall member such as the Retaining strap 31 shown in the drawing, which extends over part of the other wall 27 of the container and part of the surface 32 of the layering 13, which in terms of area corresponds approximately to the area occupied by the edging tape 26.

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As shown in FIGS. 1, 2 and 4, the extension 3O of the binding tape 26 according to its area and its dimensions be designed so that, for example, when manually separating the container 11 and the guide strip 31 from the remainder of the film unit 10 after the treatment composition has been distributed, the extension flap 30 over the edge of the previously covered by the guide strip 31 Layering 13 can be folded in order to further hold the layering together, for example in the event of unavoidable bends to ensure during storage and use of the developed film unit and at the same time as an image mask or picture frame for viewing the broadcast image through the image viewing area of the clear Layer 24 to serve through. However, it is preferable that the film unit is intact after the development treatment held, including maintaining the emptied container, the treatment composition now the occupies the spatial position assumed during developmental treatment. In this case the treatment composition should have the necessary adhesiveness both in the liquid and in the dry state to ensure cohesion and to ensure the stability of the spatial arrangement.

In general, according to a particularly preferred embodiment, the treatment composition 12 in the dispensed state is intended to be a have sufficient opacity to permit further exposure of the silver halide emulsion or emulsions of the film unit by actinic radiation incident on the transparent layer 24a during the processing of the film unit in the presence of actinic for the emusion or emulsions

to
Prevent radiation. Therefore, the development treatment of the film unit after the recording exposure can be carried out in the presence of such radiation, since the silver halide emulsion (s) of the laminate are properly protected against incident radiation

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on one major surface through the opaque layer or layers 20 and on the other major surface through the opaque treatment composition 12, as will be described below. If the edging tapes are also opaque, as explained, entry of incident actinic radiation from the edge to the emulsion or emulsions is also avoided. The opaque treatment composition and the opaque layer or layers 2Oy ¹ Bb should be selected so that they simultaneously provide a background suitable for viewing the relevant dye developer transfer image formed in the dyeable polymer layer, although in principle any opaque treatment composition and permeable to it opaque layer can be used, the treating composition and layer are preferably selected so as not to compromise the color integrity of the dye transfer image contained in the receiving layers as presented to the viewer; Particularly preferred are such an opaque treatment composition and opaque layer which are aesthetically pleasing to the eye and do not form a background noise signal which deteriorates or interferes with the information content of the dye image concerned. Particularly desirable are those opaque compositions which provide a white background for viewing the transfer image in question, especially those compositions such as are suitable for use as a background for photographic prints to be viewed in reflection, in particular layers with the optical desired for reflection of the incident radiation Properties.

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The opaque layer can in principle ^ of any contain opacifiers compatible with the photographic system in question, such as barium sulfate, Titanium dioxide, barium stearate, silver flakes, zirconium oxide and The like contained in a polymeric matrix or binder permeable to the treatment composition such as Gelatin, polyvinyl alcohol and the like may be dispersed.

A particularly preferred opaque layer comprises titanium dioxide because of its extremely effective reflective properties on. In general, a coating composition can consist of, for example HydroxyäthylZellulose are used, the titanium dioxide in sufficient quantity to achieve a reflectivity of about 85-90%. In the particularly preferred Embodiments therefore see the percent reflectivity are on the order of greater than about 85%.

If the opacifying capacity of a titanium dioxide, for example containing layer is to be increased above the usual value, an additional opacification or Opacifiers such as carbon black in a concentration of about 1 part carbon black per 100 to 500 parts titanium dioxide in the Layer can be provided. Preferably, however, this additional opacifying or opacifying capacity is created by that the opacification layer is composed of several more or less discrete layers, the the layer facing the transparent support is a reflective layer and the subsequent layer (s) is a or contain several opacifying or opacifying agents whose opacifying power is stronger than usual caused by the reflection means (s).

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As such an additional opacifying or opacifying agent Any of a variety of such opacifiers known to those skilled in the art can be used, such as for example carbon black, iron oxide, titanium (III) oxide, titanium (III) hydroxide and the like Preferably, those opacifiers are chosen which have a maximum opacity per unit weight possess, are photographically harmless and, according to their distribution, are essentially non-diffusible within "-" half of the film unit. As a particularly preferred opacifier, soot has been found to be in a concentration which, in conjunction with the respective reflection means concerned, results in the required opacity, which is undesirable physical obscuration of the particular emulsion compositions used by radiation emitted by the spread treatment composition passed through would avoid.

The liquid content of the container preferably consists of an aqueous alkaline solution with a pH and a solvent concentration at which the developer dyes are soluble and diffusible; the solution contains an inorganic light-reflective pigment in an amount sufficient to give, after distribution, a layer which has an optical transmission density greater than about 6 and exposure of the light-sensitive silver halide emulsion layers 15, 17 and "B to the dimensionally stable one Backing layer 24a prevents incident actinic radiation during development treatment in the presence of such radiation and prevents direct observation

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during dye imaging in the image receiving layer 21a and ensured after the dye transfer image is formed. The film unit can therefore after the distribution of the treatment composition in the presence of such Radiation treatment as the silver halide emulsion (s) of the film unit 10 is resistant to incident radiation are reliably protected, namely ar * the one main surface by the opaque treatment composition and on the other main surface through the opaque layer 20. If the edging tapes shown also are opaque, incident actinic radiation will also enter the emulsion (s) from the edge avoided.

As examples of for use in the treatment composition 12 suitable pigments, reference is made to the special substances given above.

A particularly preferred * opacifying agent for the treating composition is carbon black because of its highly effective light absorption properties.

In general, such opacifying aids should be used which are during and after the photographic development processing remain essentially immobile in their respective compositions, in particular should those reflective agents are used which contain insoluble and non-diffusible inorganic pigment dispersions in the composition in which they are arranged.

509811/1030

If desired, the layer 20 forming opacification aids · agents in a polymer matrix permeable to the treatment composition, such as gelatin and / or any other matrix polymers, such as those in the present invention Description specific / use as a matrix binder are given; they can also be distributed in one or more layers of the film unit that are separate from or adjacent are on or between the image receiving layer and the next adjacent silver halide layer, provided that their distribution and concentration ensures the specified masking or masking function after the development treatment; and the opacifier component of the treatment composition can finally be placed between the barrier layer 25 and the transparent layer 24a present residual of the treatment composition.

For performing a multicolor diffusion transfer process using the film unit 10, it is exposed to radiation actinic for the photosensitive laminate 13 exposed from the exposure surface 34 (Fig. 2) of the laminate.

After exposure, as can be seen from FIGS. 2 and 4, the film unit 10 is subjected to development treatment * at a suitable distance oppositely arranged rollers 33 out, which a compressive pressure on the tearable Exercise container 11, such that the longitudinal seam 28 tears and the. Treatment composition 12, which is an opacification or opacifier contains, and has a pH value which the cyan, magenta and yellow developer dyes are soluble and diffusible, between the first .Abstandsschicht 2 2a and the blue sensitive barrier layer 25 in an area of the same size as the

5 0 9 8 11/10 3 0

.4

- 28 -

called layers is distributed.

The treatment composition 12 penetrates the emulsion layers 15, 17 and 19, whereby the development of the in the Latent images contained in emulsions is triggered. The cyan, magenta, and yellow developer dyes of the layers 15, 17 and 19 are given as a function, i.e. as a function of the development of their corresponding associated silver halide emulsions, preferably essentially as a result of their conversion from the reduced form to their relative insoluble and nondiffusible oxidized form, immobilized , creating imagewise distributions of mobile, soluble and diffusible cyan, magenta and yellow developer dye formed as a function of the pixel degree of uptake exposure of the associated emulsions will. At least a portion of these imagewise distributions of cyan, magenta and yellow mobile dye developer are diffused into the

21 transfer permeable, dyeable polymer layer, such that there is a multicolor dye transfer image in this layer is generated, which can be viewed through the dimensionally stable layer 24b,

. After the transfer picture is essentially

is generated, reaches a sufficiently large proportion of the ions forming the aqueous composition 12 by way of diffusion through the for the

Composition-permeable spacer layers 22a, 22b to the polymeric acid layers 23a and 23b, which are also permeable to the composition, whereby the pH value of the solution is reduced, depending on and as a result of the neutralization, to a pH value at which the cyan, magenta

50981 1/1030

and yellow developer dyes are essentially insoluble and nondiffusible in their reduced form, such / that increased stability of the multicolor dye transfer image is guaranteed.

After the treatment solution 12 has been distributed, as mentioned above, the container 11 can optionally be removed by hand from the remaining film unit are separated.

As also mentioned above, this is multicolored dye transfer image according to that set out above preferred embodiment of the invention both during as well as after the transfer image formation through the dimensionally stable transparent layer .24b viewable.

Specific examples of the film unit according to the invention and the method according to the invention for color image formation by the dye diffusion transfer process described. These illustrative examples are not of any restrictive nature to.

For the production of film units of the one shown in the drawing Art can for example be consecutively on a first transparent polyester film carrier of ^ -thousandths Inch thick, apply the following coats:

1. The partial butyl ester of polyethylene / maleic anhydride copolymer, as a polymer acid layer 2 ^ b with a Sohiohtbelichtung of about 2500 mg / foot.

5 0 9 811/10 3 0

2. A time-delay layer comprising a 60/30/4/6 interpolymer of butyl acrylate in a ratio of about 49: 1, Diacetone acrylamide, styrene and methacrylic acid as well as polyacryl · ·

2 amide with a layer coverage of about 500 mg / foot contains, (as spacer layer 22 b)

3. A 2: 1 weight ratio mixture of polyvinyl alcohol and poly-4-vinylpyridine with a layer coverage

2
at about 400 mg / foot, as a polymeric image receiving layer (21)

4. A 25: 1 mixture of titanium dioxide and one 6o / 30/4/6 mixed polymer of butyl acrylate, diacetone acrylamide,

. Styrene and methacrylic acid, with a layer coverage of about 1800 mg / foot.

5. Gelatin at a layer coverage of about 50 mg / foot.

6. A mixture in a weight ratio of 1: 0.8: 0.1 of carbon black, Rhoplex E-32 (an acrylic latex sold by Rohm and Haas Co., Philadelphia, Pa./USA) and polyacrylamide, with a? ¹ layer coverage of approximately 240 mg / foot measured as carbon.

7. A mixture in a weight ratio of 1: 1 from (a) a solid dispersion of cyanogenerating dyes

509811/1030

HC-NH-O ₂ S ('

CH.

SO ₂ -NH-CH

Gelatine and polyvinyl hydrogen phthalate in layers

with a layer coverage of about 6] mg / foot, removal

P P

wiekler dye, about 97 mg / foot gelatin and about 5 mg / foot Polyvinyl hydrogen phthalate, and (b) a red sensitive Gelatine / silver iodobromide emulsion in layers - with a Layer coverage of about 67 mg / foot of silver iodobromide (

P "

measure as silver) and about 29 mg / foot of gelatin.

8 .. A red-sensitive gelatin-silver iodobromide emulsion and Polyvinyl hydrogen phthalate applied in layers with a

Layer coverage of about 62 mg / foot of silver iodobromide (

measure as silver), about 60 mg / foot gelatin and about 0.8 mg /

ρ

Base polyvinyl hydrogen phthalate.

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9. A layer of butyl acrylate / diacetone acrylamide / styrene /

Methacrylic acid (60/30 / V6) and polyacrylamide in layers in a ratio of about 29: 1, with one layer

coverage of approximately l62 mg / foot.

10. A mixture in a weight ratio of 1: 1 of (a) a solid dispersion of the magenta developer dye

₂ V

N — SO

(II)

OH

and gelatine in layers with a layer coverage of about 100 mg / foot of the dye developer and about 87 mg /

Feet of gelatin and (b) a green-sensitive gelatin-silver iodobromide emulsion applied in layers with a layer coverage of about 20 mg / foot of silver iodobromide (measured as silver) and about 22 mg / foot ^{2 of} gelatin.

11. A green-insensitive gelatin-silver iodobromide sulfone and • Polyvinyl hydrogen phthalate applied in layers with a

Layer coverage of about 40 mg / foot of silver iodobromide (

measure as silver), about 87 mg / foot of gelatin and about 1.3 mg /

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Base polyvinyl hydrogen phthalate.
12, a layer of butyl acrylate / diacetone acrylamide / styrene /

Methacrylic acid (60/50 / V6) and polyacrylamide in layers in a ratio of about 29ϊ4, with a layer coverage of about 110 mg / foot and succindialdehyde in the layer

application with a layer coverage of about 10 mg / foot

15. A mixture in a weight ratio of 1: 1 of (a) a solid dispersion of the yellow developer dye

Cr-H ₂ O

-C-CH ₂ -CH ₂

OH

(in)

and gelatin in layers with a layer coverage

2 p

from about 120 mg / foot of developer dye and about 48 mg / foot Gelatin, and (b) a blue-sensitive gelatin-silver iodobromide emulsion and coated polyvinyl hydrogen phthalate at a coating coverage of about 50 mg / foot silver

ρ jodbromi ^ (measured as silver), about 22 mg / foot of gelatin

and about 0.3 mg / foot polyvinyl hydrogen phthalate.

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14 A blue-sensitive gelatin silver iodobromide emulsion, polyvinyl hydrogen phthalate and 4'-methylphenyl hydroquinone in N ^ M diethyl lauramide in layers with a layer

coverage of about 100 mg / foot of silver iodobromide (measured as silver), about 66 mg / foot of gelatin, about 0.6 mg / foot of polyvinyl hydrogen phthalate, and about 25 mg / foot 4 ^! - “Methylpheny! Hydroquinone.

15. A layer of butyl acrylate / diacetone acrylamide / styrene / Methacrylic acid (60/30/4/6) in a layer application with a layer

^% coverage of about 100 mg / foot.

A second clear polyester film base of 4 thousandths Inch thickness is then applied to this laminated photosensitive element at its side and rear ends by means of a self-adhesive edging tape when pressure is exerted, this is stuck along the edges of the laminate thus formed and this extends overlapping.

Then a tearable container, which has an outer layer made of lead foil and an inner lining or inner layer made of polyvinyl chloride and contains an aqueous alkaline treatment solution, is attached to the front edges of the two partial layers by self-adhesive tapes which connect the containers and layers in question to one another, in such a way that at Pressure exerted from the container, its contents after the edge seam of the container between the second transparent polyester film carrier has been torn open. and the next adjacent layer 15 is distributed. The following composition, for example, can be used as the aqueous alkaline treatment solution contained in the tear-open container: about 0.8 cm3 of 0.5 cm3 of 1N sodium hydroxide and about 0.8 cm3 of water, about 100 cm3 of 10.5 g of potassium hydroxide , about 2.3 g of carboxymethyl cellulose, about 96.5 gj titanium dioxide, about 2.9 g of N-benzyl-a-piccolinium bromide, about 1.7 g of N-phenetyl-a-piccolinium bromide, about 2 g of an aqueous silicon dioxide dispersion with about 30 % SiOj content, as well as one or more antifoggants, such as 15 g benzotriazole,

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and about Ο, θ6 g of o-methyl ^ -bromo - ^ - azabenzimidazole, about 0.67 g 6-methyluracil, about 0.47 g of bis (-aminoethyl) sulfide, about 0.94 g of 6-benzylaminopurine, about 1.22 g of polyethylene glycol, about 1.9 g of 1-hydroxyethylethylenediamine-tetraacetic acid, about 0.22 g Lithium nitrate and about 0.25 g lithium hydroxide.

The composite photosensitive film units can exposed to radiation incident on the transparent polyester film support and for the development treatment of the exposed Film units by suitable press members such as from 5p to 60 thousandths of an inch for example, those arranged opposite one another at a suitable distance Rollers are guided, whereby the container is torn open and its contents' is distributed. After the development treatment, the formation of the multicolored Dye transfer image through the first clear polyester layer against a titanium dioxide reflective layer to be observed.

Film units produced in the manner described above can be processed in the manner indicated after exposure through a conventional step wedge in order to obtain a graphical illustration of the characteristics of the individual dye transfer images forming the multicolor dye negative images. In detail, the detailed characteristics can be determined by using the density of the images in question when exposed

and
red, green γ blue light as a function of the logarithm of the exposure of the photosensitive element; in this way, for example, the characteristic cyan, magenta and signal transmission image dye curves (as read against red, green and blue reflected light) of the test and

509811/103 0

Control film units.

By adding the substances mentioned below in effective concentrations to the treatment composition:

18 ^H 37 " ⁿ

(IV)

and

(V)

S09811 / 1030

for example in amounts of 6.17 and 1.37 S to the second Component of the treatment composition specified above. · Can be achieved that the image formation in the

Receiving layer immediately after distribution the treatment composition, as a result of the optical transmission density of more than 6 density units of the composition provided protection of the photosensitive silver halide emulsion layers against incident radiation and against that caused by the optical reflection density of the composition effective titanium dioxide reflective background guaranteed by less than one density unit.

The barrier layer 25 provided according to the present invention, detailed above with regard to its structure, permeable to the treatment composition but impermeable to the image dye, on the one hand, leaves the liquid treatment composition including the treatment agents contained therein, whose molecular dimensions are smaller than those of the stated yellow-magenta and cyan -Developer dyes, pass through, but at the same time prevents the passage or extraction of developer dye dissolved in the processing composition from the photosensitive laminate into the processing composition, as would otherwise occur as a result of the differential dye concentration gradients between the laminate and the initial introduction and distribution point of the processing composition and as a result of the Dye Sinking Capacity of Processing Compositions Commonly Used in Photographic Dye Fusion Transfer Processes a would occur. By limiting the diffusion of the dye during the development treatment of the film unit on the photosensitive laminate, one achieves higher efficiency and economic advantages due to the lower amount of dye required per unit dye transfer density of the resulting transfer image, and also optimal control and control of the amount of dye used by the associated Silver halide weight as a function of the degree of point-by-point exposure of the

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Layer with actinic radiation, resulting in increased sharpness of the dye transfer image produced.

As examples of additional polymer compositions specific to the treatment composition provided according to the invention permeable, for the dye developer during the effective development treatment period one Film unit of the type mentioned above, however, impermeable layer ■ the following compositions may be mentioned as examples: butyl acrylate / diacetone acrylamide / s tyr ol / methacrylic acid (6o / j5O / 4/6) + Polyacrylamide at 1 to 2 percent by weight of the tetrapolymer, applied in layers with a layer coverage of about 100 mg / foot J Butylaor jlat / diaze tonacrylamid / s ty rol / methacrylic acid (6o / j5O / 4/6) + Polyvinyl alcohol) in a ratio of 10: 1 in a layer application

with a layer coverage of about 100 mg / foot; 2-sulfoethyl methacrylate / ethyl acrylate / methacrylic acid; Rhoplex E-32, HA-12 or ΗΑ-ΐβ (trade name used by Rohm and Haas Co., Philadelphia, Pa./USA for certain acrylic latexes + less than 1 % polyacrylamide! Etc.

50981 1/1030

3441751

The pH and the solvent concentration of the alkaline developing treatment solution are selected to suit them initially preferably a pH value above the pKa of the optical filter medium (if such filter medium is used are), i.e. the pH at which about 50% of the filter media is in the less absorbent form and about 5o% are in the more absorbent form, before-

about preferably a pKa value of more than yTI and particularly preferably of more than γ! δ , at which pH the developer dyes are also soluble and diffusible at the same time. Although the particular pH value to be used for any given developer dye and any desired optical filter medium or group of developer dyes and filter media can easily be determined empirically, it has been found that the particularly preferred developer dyes, in reduced form, at pH values above 9 are soluble and relatively insoluble at pH values below 9 and the system can easily be adapted to such developer dyes. Furthermore, as mentioned above, according to the preferred embodiment, the treatment composition can comprise one or more viscosity-increasing film formers, whereby the distribution of the composition and its cohesion after distribution as a structurally stable layer of the laminate are facilitated, albeit. the use of such an agent as a component of the developing composition is not absolutely necessary. In this last-mentioned case, ie if the composition does not contain a separate film former, it is preferable that the concentration of the solvent used for the composition, i.e. the water, etc., has the lowest possible minimum value necessary for carrying out the transfer process, so that the structural *

50981 1/1030

2U1751

constructive cohesion of the laminate is not impaired and the layers forming the laminate the Can absorb and distribute solvents without difficulty during development treatment and drying, without undesirable dimensional changes occurring in the layers forming the laminate.

As set out in the aforementioned patents, the liquid treatment composition intended for the multicolor diffusion transfer process comprises at least one an aqueous solution of an alkaline substance, for example diethylamine, sodium hydroxide or sodium carbonate and the like and preferably has a pH of more than 12? according to a particularly preferred embodiment, it has a viscosity-increasing compound acting as a film-forming agent, which after the development composition has spread and dried forms a relatively strong and stable film. As preferred film formers are suitable high molecular weight polymers, such as polymeric water-soluble ethers, which are in an alkaline solution, such as a hydroxyethyl cellulose or sodium carboxymethyl cellulose are incorporated. Film formers also come or thickeners whose viscosity-increasing capacity remains essentially unaffected if they are used for a long time be kept in solution. As mentioned, the film former is preferably in the treating composition in such amounts provided that the composition have a viscosity greater than 100 cps, and preferably on the order of 100,000 cps to 200,000 cps, at a temperature of about 24 ° C.

509811/1030

As mentioned, the film unit of the present invention has a Neutralizing device, for example a polymer acid layer of the kind explained above, by means of which the alkalinity of the treatment solution from a pH value at which the dyes are soluble as a function of the exposure exposure of the film unit, and which optionally over the pKa of the optical filter media used a pH value is reduced which is below the pKa value of the respective filter medium and at which the coloring ' Substances are essentially non-diffusible in order to be more advantageous Way to ensure further stabilization * and optimal 'reflectivity of the dye transfer images. The neutralizing layer may be an acidic reagent disposed in particulate form in the film unit a polymer acid layer, for example a polymer acid layer about 0.3 to 1.5 thousandths of an inch thick, the arranged between the first / or the second transparent carrier layer and the next adjacent functional layer is; the film unit can also include a polymeric spacer or barrier layer of, for example, about 0.1 to 0.7 thousandths of an inch thick closest to that of the subject Have polymeric acid layer or layers and opposite the relevant carrier layer, as described above.

In particular, the film units can comprise a polymeric acid layer as described, for example, in US Pat. No. 3,362,819 have what, in a particularly preferred manner, the presence

twelve See means an inert time delay or spacer layer / the polymer acid layer arranged on a carrier layer and the image-receiving layer.

As mentioned, the pH of the treatment composition is preferably on the order of about 12 to 14, and accordingly

509 81 1/103 0

the pKa value of the particular optical filter medium used is preferably of the order of 12 or more. The polymer layer contains at least sufficient acid groups to lower the pH. _: effecting the image layer from a pH of about 12-14 to a pH of at least 11 or less at the end of the soak period; preferably, the pH should be lowered to a value of about 5 to 8 within a short time after soaking, it being necessary, of course, to precisely control the action of the polymeric acid so as not to cause negative image formation or image transfer of the non-oxidized developer dyes. For this reason, the pH of the image overlay must be maintained until the dye image / functional transfer level is obtained, e.g. to at least about 11 and preferably about pH 9 to 10. Non-oxidized developer dyes, which contain hydroquinonyl developer radicals, diffuse as a sodium or other alkali salt from the negative to the positive and the pH of the image-receiving layer is required to remain on the order of, for example, 12-14 until the required amount of dye has been transferred. In addition to the desired effect on the light stability of the image, the subsequent reduction in pH also fulfills an extremely valuable photographic function in that further dye transfer is thereby essentially completed.

In order to prevent a premature lowering of the pH value during the transfer process, as it would express itself, for example, in an undesirable * reduction * in the density of the positive image , 'Are the acid groups in the polymer layer so yer-

50981 1/1030

shares that the extent and rate of their availability and accessibility for the alkali is controllable, for example as a function of the swelling speed of the polymer layer, which in turn is directly related to the elution speed the alkali ions. The type of availability of the acid groups in the polymer layer which is desired in each case can thereby be determined achieve that you polymeric acid with one of acidic groups free or such acidic groups containing only a lower concentration, compatible with the acid polymer to a modified polymer System mixes, or by using only one acidic polymer, but selecting one, 'the one has predetermined availability of the acid groups according to extent and speed. ''

The layer containing the polymer acid can also be a water-un- · soluble polymer, preferably cellulose ester, which can control or influence the speed with which the alkali salt of the polymer acid is formed. As examples Cellulose acetate, cellulose acetate butyrate, etc., may be mentioned of cellulose esters which may be used for this purpose. The fir a particular embodiment of the specific polymers and polymer combinations used in each case will of course be so chosen so that they have suitable wet and dry strengths; if necessary or if necessary, suitable backing layers are used to ensure the mutual adhesion of the polymer layers to ensure each other during storage and use.

The inert spacer layer according to the last mentioned patent, for example an inert spacer layer of polyvinyl alcohol or gelatin, acts as a "timing controller" for the pH reduction through the polymer acid layer. This timing is done as a function of the extent and speed, with

509811/1030

which the alkali diffuses through the inert spacer layer. As indicated in the referenced US patent found that the pH drops only after the alkali has permeated the spacer layer, i.e. the pH drops through the mere diffusion into the intermediate layer has not yet been significantly reduced, but it falls off very quickly as soon as the alkali diffused through the spacer layer.

As detailed in the referenced U.S. Patent 3,362,819 apart causes the presence of an inert spacer layer an equalization of the different reaction rates over a wide temperature range, for example by a premature pH decrease is prevented if the impregnation takes place at temperatures above room temperature, for example occurs at temperatures of 95 to 100 ° F. As set out in the cited patent, the use of a Inert spacer layer achieves that the extent and rate at which alkali is trapped in the polymeric acid layer available to be a function of alkali diffusion rates.

However, as explained in US Pat. No. -3,455,686, this rate at which the cations of the alkaline processing composition, ie the alkali ions, are available for trapping in the polymeric acid layer, should preferably decrease as the temperature of the diffusion transfer development treatment increases, in order to allow the color photographic process to take place To ensure diffusion transfer process that is relatively independent of fluctuations in positive image transfer within a wide range of ambient temperatures.

In detail in the aforementioned U.S. Patent 3 4 55 686 it is stated that the diffusion speed of alkali increases by an alkali-permeable inert polymer spacer layer with increasing processing temperature to such an extent that

50981 1/1030

for example at relatively high transfer development temperatures, i.e., at transfer development temperatures above about 80 ° F, a premature drop in the pH of the Transfer development composition takes place, at least in part due to the rapid diffusion of the alkali from the field of dye transfer and its subsequent Neutralization on contact with the polymer acid layer. It

it has been found that this is especially true for alkali when passing through

occurs / an inert spacer layer applies whose alkali permeability its effect is optimally coordinated with the temperature range of the optimal diffusion transfer treatment. »Vice versa provides diffusion transfer treatment at temperatures below this optimal range, for example at temperatures below about 40 ° F, the aforementioned inert spacer layer provides an effective temporal diffusion barrier that allows enforcement the inert spacer layer by alkali with reduced diffusion rates due to the low temperature " effectively prevents what leads to the high pH in the area the diffusion transfer treatment is maintained for an extended period of time, thereby creating a Spotting in the transfer image and the resulting deterioration and impairment of the color definition of the Transfer positive image can be facilitated. ®

However, as also shown in US Pat. No. 3,455,686, the impairment of the positive transfer image resulting from the aforementioned prolonged maintenance of the pH value and / or the premature pH reduction can be avoided if the inert ones are used. The spacer layer of the positive print-receiving element is replaced by a spacer layer, which is a polymer layer permeable to alkali, the permeability of which depends reciprocally on the temperature, i.e. when using a polymer film-forming agent, the permeability for dissolved alkali decreases with increasing temperature

50981 1/1030

have derived cations such as alkali metal and quaternary ammonium ions.

Examples of substances suitable for use as an image receiving layer are suitable are polymers which can be dyed from solution, such as nylon, for example N-methoxymethyl-polyhexamethylene-adipamide; partially hydrolyzed ·· polyvinyl acetate; Polyvinyl alcohol with or without plasticizers; Cellulose acetate with bulking agents such as half cellulose acetate and half oleic acid; Gelatin ^ as well other substances of a similar nature. Preferred substances are polyvinyl alcohol or gelatin with a dye mordant such as, for example Poly-4-vinylpyridine as described in US Pat. No. 3,148,060.

The developing treatment liquid can be an auxiliary developing agent or contain a development accelerator, such as.

.. * for example p-methylaminophenol 2,4-diaminophenol, p-benzylaminophenyl-y Hydroquinone, Toluhydroquinone, Phenylhydroquinone, V -Methylphenylhydroquinone, etc. One can also use several such Use developer adjuvants or developer accelerators, such as a 3-pyrazolidone developer and a benzoid developing agent, see US Pat. No. 3,039,869. As examples of suitable combinations of

- Developer auxiliary substances may be mentioned 1-phenyl-3-pyrazolidone with p-benzylaminophenol and 1-phenyl-3-pyrazolidone with 2,5-bis-ethyleneimino-hydroquinone. Such auxiliary developing agents can be used in the liquid processing composition or they can be at least partially in one or more of the silver halide emulsion layers, in in the layers containing the developing dyes, in the intermediate layers, in the image-receiving layer or in any one of them other auxiliary layer or layers of the film unit may be incorporated.

It should be noted that at least a portion of the developing dye oxidized during development as a result of a

50981 1/1030

Reaction, for example an energy transfer reaction, with the oxidation product of an oxidized auxiliary developer substance can be oxidized and immobilized, this developer aid s substance has been oxidized by the development of exposed silver halide. Such a reaction of an oxidized Auxiliary developer with non-oxidized dye developer would act as the auxiliary developer for further reaction regenerate with the exposed silver halide.

Furthermore, the development in the presence of an onium compound, in particular a quaternary ammonium compound, by the process described in US Pat. No. 3,173,786.

Of course, the relative amounts and proportions of the components of the diffusion transfer treatment composition can be varied as required. Thus, without departing from the scope of the invention, the developer compositions described above can be modified by the use of preservatives, alkalis etc. other than those specifically mentioned above, provided that the pH of the composition is initially at the required initial pH. If necessary, the developing composition may also contain ingredients such as retarders, accelerators, etc. Likewise, the concentration of the various constituents can vary within a wide range; if desired, suitable ingredients in the photosensitive layer can be placed in a separate permeable layer of the photosensitive element and / or prior to recording exposure. or in the photosensitive emulsion.

For the mentioned Qimensionsstabilen layers or sheets, any variety of conventional transparent, rigid or flexible suitable materials, for example, both synthetic as well

50981 1/1 030

papers and polymer films derived from natural products. It Substances impermeable to alkali solutions, such as methyl and ethyl esters of polymethacrylic acid, can be used; Vinyl chloride polymers, polyvinyl acetate, polyamides such as nylon; Polyesters such as polymeric films of ethylene glycol and terephthalic acid; Cellulose derivatives such as cellulose acetate, cellulose triacetate, nitrate, propionate, butyrate, acetate propionate or acetate butyrate. It should be noted that one or more of the specified layers can be dispensed with if the others Layers of the laminate can take over the functions of these layers that are to be omitted, for example when the remaining layers of the laminate have the required dimensional stability and radiation filtering properties.

In all examples of the present description, percentages are given; of components, unless expressly stated otherwise, are percentages by weight.

While the invention has been described in detail throughout, it has been based on the use of developer dyes as the preferred color formers explained; of course, however, other, less preferred, dye images can be produced according to the Substances producing diffusion transfer processes in place of the preferred developing dyes can be used in the practice of the invention. For example, color formers, i.e., dye-image-forming substances according to the following U.S. patents are used: 2,647,049,

2 661 293, 2 698 244, 2 698 798, 2 802 735, 8 148 062,

3,227,550, 3,227,551, 3,227,552, 3,227,554, 3,243,294, 3,330,655, 3,347,671, 3,352,672, 3,364,022, 3,443,939, 3,443,940, 3,443,941, 3,443,943, etc .; in these patents are color diffusion transfer processes using Color coupling methods described in which at least partially

50981 1/1 030

_we ise one or more color developing agents and one or more dye image-forming couplers, color former or be brought to form a dye transfer image in an overlying image-receiving layer to the reaction. Color formers according to US Pat. Nos. 2,774,668 and 3,087,817 can also be used; in these patents color diffusion transfer processes are described in which the image-correct differential transfer of complete dyes according to the mechanisms described therein is used to transfer a dye image into an adjacent image-receiving layer; this includes "the use of dye-image-forming substances which are completely or partially insoluble or non-diffusible initially in the state in which they are arranged in the film unit and which diffuse during the development treatment as a direct or indirect function of the exposure exposure.

If desired, the film unit can also be UV absorbing Substances to protect the stained dye transfer image contain against fading by UV light; for example, substances from the general class of benzotriazoles come for this purpose and benzophenones such as those mentioned in U.S. Patents 3,004,896 and 3,189,615 2-phenyl-benzotriazole agents, etc. are eligible; the 2-hydroxybenzophenones such as, for example, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone etc.; substances soluble in both water and organic solvents are possible; and or Brightener b, betw. Shine agents like those from the general class the triazine stilbenes, coumarins, anthracenes, terphenyls, tetraphenylbutadienes Quinoxalines, such as those used as conventional fluorescers and as conventional optical brighteners or brighteners

are known. Suitable triazine stilbene brighteners or brighteners are described in U.S. Patent 2,933,390, coumarins in British Patent 786,234, and various other agents in U.S. Patent Nos. 2,171,427, 2,473,475, 2,595,030, 3,660,578 , as well as British patents 595 065, 623 849, 624 051, 624 052, 678 291, 681 642, 705 406, etc. Commercial brighteners or brighteners are available under the names Tinopal (SP, WR, SFG, BV277, 2B, q $, NG), Leucophor B, Calcoflour White MR, Blandofor SC, Hitamine (BSP, N, SOL, 6T6) and the like are commercially available, correspondingly commercially available UV absorbers under the name Tinuvin and the like.

Generally speaking, the UV absorbers and optical brighteners can vary within a wide range Concentrations are used. Appropriate concentrations

ip:, 2

2 range from about 0.2 to 10 mg / foot of image receiving area and preferably between about 1 to 5 mg / foot '

Said means can be in one or more layers of the film unit, preferably between an opaque one Layer, which forms the background against which the image is viewed, and the viewing surface in any desired way Wise incorporated, for example as a component of the casting and / or coating solution or the preparation this layer bsw. Layers with an organic solvent or water as a carrier or as a latex dispersion used composition.

In the cases where the image receiving layer or layers has sufficient dimensional stability to form a self-supporting layer, this can optionally be transferred to a suitable one dimensionally stable carrier layer be applied, this

K09811 / 1030

- 51 -

Carrier layer to a type or a class of the type mentioned in this description and also to another type can belong.

If the image-receiving layer than on a separate dimensionally stable Support layer arranged layer is formed / it will usually have a thickness on the order of about 0.1 to 0.4 thousandths of an inch, while they are of the order of magnitude when formed as a self-supporting layer of 3 - 6 thousandths of an inch.

Except for conventional methods of directly dispersing a particulate matter in a polymeric or colloidal matrix such as The preparation of the developer dye and color coupler dispersions can also be prepared in the ball mill and the like Wise done that one dissolves the dye and / or coupler in a suitable solvent or solvent mixture and the solution thus obtained is distributed in the polymeric binder, optionally then the one or more Solvent can be removed, for example by evaporation, if the solvent (s) in question has a sufficiently low boiling point, or by washing out, if the solvent or solvents have a sufficiently strong different solubility in the washing medium / for example Water compared to the solubility of the remaining components of the composition; after all, the The dispersion can also be prepared in such a way that both the polymeric binder and the dye are in dissolves a common solvent; Finally, a combination of these production methods can also be used.

For further detailed treatment of solvent distribution systems of the types described above , as well as

509811/1 030

for a detailed compilation of conventional, traditional

to the
For the distribution of photographic color former substances in polymeric binders, in particular solvents used to produce the partial layers of photographic film units, reference is made to US Patents 2,269,158, 2,322,027, 2,304,939, 2,304,940, 2,801,171 and so on.

For the preparation of the photosensitive gelatin silver halide emulsions for use in the film unit, the silver halide crystals can be prepared as follows procedure: Reaction of a water-soluble silver salt, such as silver nitrate, with at least one water-soluble one Halide, such as ammonium, potassium or sodium bromide, preferably together with a corresponding one Iodide, in an aqueous solution of a peptizing agent such as a colloidal gelatin solution; digesting the dispersion at an elevated temperature to increase crystal growth; Washing the obtained water-soluble Salts by quenching the dispersion, further noodling the settled dispersion and washing the pasta with cold water or alternatively by using the various flocculation systems or methods for effective Removal of unwanted components, for example the method according to US Patents 2,614,928, 2,614,929, 2,728,662 and the like; Post-ripening of the dispersion at elevated temperature in conjunction with the addition of gelatin and various Additives, for example chemical sensitizers according to US Patents 1,574,944, 1,623,499, 2,410,689, 2,597,856, 2,597,915, 2,487,850, 2,518,698, 2,521,926, etc. All these measures are carried out according to the usual conventional Processes carried out, for example, in Neblette, CB., Photography Its Materials and Processes, 6th Ed., 1962.

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The optical sensitization of the silver halide crystals The emulsion can be rotated by contacting the emulsion composition with an effective concentration of the particular selected optical sensitizing dyes dissolved in a appropriate dispersants, such as methanol, ethanol, acetone, water and the like., Take place in the in a very conventional manner, as described, for example, in Hammer, F.M., The Cyanine Dyes and Related Compounds.

If necessary, additional additives such as coating aids, Hardeners, viscosity-increasing auxiliaries, stabilizers, preservatives and the like, such as those in the agents listed above, are also incorporated into the emulsion mass, accordingly the usual methods known for the preparation of photographic emulsions.

As described above, the light-sensitive material of the photographic emulsion preferably contains a silver crystal, for example one or more silver halides, such as silver chloride, silver iodide, silver bromide or mixed silver halides such as silver chlorobromide, silver chloroiodobromide or silver iodobromide, in different halide ratios and with different silver concentrations.

As far as the binders for the emulsion layers concerned are concerned, the gelatin mentioned can be replaced in whole or in part by another colloidal material, for example albumin, casein or zein, and also by resins, such as cellulose derivatives, according to US Pat. No. 2,322,085 and 2 327,808, polyacrylamides according to US Pat. No. 2,541,474; and vinyl polymers, such as they are described in a large variety of US and foreign patents.

rnnn 1 1/1 Π 0 fi

It is true that the invention has been explained above with reference to a preferred structure of the photosensitive component which at least two selectively sensitized photosensitive Layers are coplanar and in particular the explanation has been given on the basis of the preferred Tripack structure with a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, each with a cyan developer dye, a magenta developing dye and a yellow developing dye are associated therewith; however, the photosensitive grain ' component of the film unit also includes at least two groups of selectively sensitized very small photosensitive Elements contained in the form of a photosensitive grid arrangement, each being each of the tiny photosensitive Elements, for example, a suitable color former in or behind its corresponding silver halide emulsion section assigned. Generally speaking, such a photosensitive screen can contain small red-sensitized emulsion elements, small green-sensitive emulsion elements as well containing small blue-sensitive emulsion elements in side-by-side arrangement according to the grid pattern, with the elements one cyan, one magenta and one yellow developer dye is assigned.

also —the use The invention relates to / to / a black image-forming agent Dye material and the use of a mixture of, for example, developer dyes ^ which produce a black and white transfer image result, for example, the use of developer dyes of the three subtractive colors in suitable mixture in which the respective amounts of the developer dyes are adjusted so that the colors combine with black.

The ^{term M} used in the description is positive image "

5Π9811 / 1030

not to be understood in a limiting sense; it is used for illustration only and designates the _{image formed in the B 4} image receiving layers as being reversed in the positive-negative sense to the image in the photosensitive emulsion layers. As an example of a different meaning of the term "positive image" in this general framework, it is assumed that the photosensitive element is exposed to actinic radiation through a negative slide. In this case the latent image in the photosensitive emulsion layers would be a positive image and the dye image formed in the image receiving layers would be a negative image. The term "positive image" is intended to include such an image generated in the image-receiving layer. Of course, in addition to the essential layers described, the film unit can contain multiple coatings, bases or layers, which in turn may contain one or more additives such as plasticizers, between essential layers, for example to improve adhesion; It should also be emphasized that one or more of the layers described can consist of two or more layers of the same or different components which lie against one another or can also be separated from one another, for example two or more neutralization layers or the like.

In the preferred embodiment shown in the drawing and described above, the sheet or film 24a is transparent and covers the entire surface of the exposure surface of the photosensitive laminate; if desired, however, it can also be provided that the sheet or the foil 24a is not placed on the laminate until after the photo-exposure of the film unit; for this purpose it can be provided, for example, that the sheet or the film is at its leading edge on a transverse leading edge of the photosensitive laminate

50981 1/1030

is attached and is adapted to be used after photo-exposure at least during the development treatment on and completely covering the exposure surface of the laminate can be placed in order to distribute the treatment composition, for example after the container has been torn open and the directional emptying of the treatment composition contained therein over the exposure surface of the laminate facilitate. In such an embodiment, the removable sheet or film can either be transparent or opaque and the treatment composition may or may not contain an opacifying agent as desired by the user not. After the treatment composition has been distributed, the sheet or foil can be removed by hand from the remainder of the film unit be separated, either alone and / or in combination with the treatment composition used and / or the used tearable container of the treatment composition.

According to a preferred embodiment of the invention, has the film bandage for producing a positive dye print to be viewed in reflection, a light-sensitive film unit as described above, specifically for development in the presence of ambient radiation and for viewing the Dye-reflective positive print during and after development treatment is formed without separating the constituent parts of the film unit; she assigns guiding devices

509811/1030

mutual connection of film units and optionally on * successive removal of the film units from a film pack or magazine, and preferably a whole or partially arranged in the treatment composition opacifying or opacifying agent, which together with the opaque layer exposes the photosensitive material in the first sheet member of the film unit prevented by actinic radiation incident on the film unit in its development treatment state.

A preferred embodiment of one of the film units described Containing film packs or magazines has several film assemblies in one for individual exposure exposure each of these film dressings in a camera suitable form in an initially light-tight container, which the successive exposure of the film units allowed · *. The container has a front wall with a translucent one Section, for example an exposure. · Opening and an opening in a wall through which the film associations can be pulled out individually. The photosensitive film units are collectively in the form of a stack placed in the container below the exposure opening, with the exposure area of each film unit on top and the tear-open container is arranged adjacent to the opening through which the film units are removed, in such a way that in each case after the recording exposure of each film unit this by pulling on the guide member of the film unit set in motion and through the opening out of the container is pulled out. The film pack is initially provided with a cover member or sheet that resides in the container is attached and extends over the exposure opening in order to seal it against the entry of light. This deck element also has one out of the container through the removal opening

50981 1 / 10-30

protruding guiding element that can be pulled out through this.

For use, the film pack is inserted into a camera, which has two opposing pressure-exerting organs, in such a way that that the removal opening comes to lie adjacent to the pressure exertion organs and the exposure opening approximately in the Image or exposure plane of the camera. The guide member or the guide strip for the cover element is outstanding the pack and out of the camera over, in such a way that the cover element by gripping the guide member and pulling on it the pack can be pulled through the pressure exerting organs and out of the camera for the selective exposure exposure of the individual film units of the pack. After the respective exposure of each successive Film units is the respective film unit individually for itself out of the container and through between the pressure-exerting elements removed from the camera by moving the guide strip of the first film unit and, accordingly, of the successive ones Pulls film units out of the container and out of the camera.

In the following, with reference to Figures 1, 8 and 9 of Drawing described film units and a film pack arrangement of such film units. Each film unit 10 has a Guide sheet 31 having a front or guide section 38 and a rear end section 40 on which the guide sheet 31 is connected to the film unit in the region of the front end thereof. The guide sheet 31 with the front and End sections 38 and 40, respectively, have approximately the same width as the film unit 10; the front portion 38 of each leader sheet, 31 is connected to the rear end of the next preceding film unit, or in the case of the first film unit, to the Cover sheet, preferably adjacent to the rear end portion

50981 1/103 0

of the previous element (cover sheet or previous film unit). The length of the guide sheet 31 between the connection point located in the area of its front end with the one film unit and that in the area its rear end junction with the next following film unit is essentially the same the length of the film units between their leading and trailing edges. The interconnected film units and Guide sheets are folded in a jagged shape.

8 and 9, a film pack composed of film units 10 according to the invention is shown. This film pack, designated as a whole by 44, has all the layer components and mechanical components, including the pressure-exerting organs, required to produce a plurality of color prints produced by the diffusion transfer process. The film pack 44 consists of a generally parallelepipedic container or box 46 which receives and encloses a plurality of film units 10 in a stacked manner. The container 46 has a front wall 48, side walls 50, a rear end wall 52 and a front end wall 54 as well as a rear wall 56 and is preferably made of an at least semi-rigid plastic material suitable for conventional molding processes. The front wall 48 is provided with a generally rectangular exposure opening 58 for the passage of light for the recording exposure of the respective foremost of the film units stacked in the container. The front end wall 54 is provided with a generally rectangular removal slot, or an outlet opening 60, the front edge of which is defined by the front wall 48 and through which the film units contained in the container can be brought out individually after the exposure. In order to better ensure that only one film unit at a time passes through the opening 60, limiting or retaining means are provided

50981 1/1030

- 6ο -

provided in the form of one or more projections or extensions 62 of the rear wall 54. The projections or extensions 62, which, as shown, form integral parts of the rear wall 54, partially protrude over the opening 60 up to places where they block the opening to such an extent that it is deformed or bent must be in order to allow the foremost film unit of the stack to pass through, i.e. the one for the exposure Allow the film unit resting against the front wall 48 above the receiving opening 58. The protrusions 62 form a resilient construction such that when the respective front film unit is removed through the opening 60, the front edge this film unit comes into abutment against the projections 62 and this so far bends outward that only this The foremost film unit can exit through the slot 60, while the next following film unit at the passage through the slot is prevented.

The film pack according to the invention

is initially provided with a dark slider or cover sheet 6 4 made of a sheet or foil material impermeable to actinic light to prevent light from entering through the exposure opening 58 before the film pack is inserted into a camera or the film pack is attached to the rear of a camera. The cover sheet 64 has a section of at least the same surface area as the front wall 48 to prevent the entry of light, as well as a. Guide or front portion 66, which, as shown, may be narrower or tapered and protrudes from the film pack and in this way forms a guide strip that can be grasped to manually pull the DecMiatt out of the film pack in order to record the exposure of the film under the To allow exposure aperture and the cover sheet stacked film units. On the front wall 48 is a

509811/1030

- 61 - ■

the exposure opening 58 surrounding lip or a raised edge 68 is provided, which in cooperation with the Camera the appropriate alignment of the film pack and its * exposure opening with respect to the exposure systems of the Camera guaranteed; in cases where the film pack is at the back attached to the camera, instead of being completely inserted into it, the lip or edge 68 ensures one at the same time light-tight seal between the interior of the camera and the interior of the film pack case.

As mentioned, the film units 10 are between the front and the back wall of the film pack are stacked one behind the other with the sheets 24a facing forward and the exposure areas of the film units with the exposure opening 58 of the film pack case are aligned. Furthermore, there are means for elastic pretensioning of the filra units 10 and the cover sheet 64 forward against the back the front wall 48 is provided, by means of which the exposure opening, as long as the cover sheet is present, light-tight is completed and after removing the cover sheet the front film unit in the appropriate one Position for the picture exposure in the image plane of the camera, i.e. against the back of the front wall 48 of the Film pack container is pressed. This resilient pretensioning device has an assembly designated as a whole by 70 Spring and pressure plate, preferably made of resilient sheet metal, with a substantially rectangular frame 72 for contact against and support of the rearmost film unit, as well as with a transverse part 74, from which prestressing spring parts 76 extend backwards to rest against the rear wall 56 of the film pack to the frame 72 and thus the of biasing this supported film units forward in the direction of the front wall 48.

50981 1/1030

As mentioned, each film unit 10 has one at its rear end 40 with the front surface near the front end the film unit connected to the guide member 31. The film units and guide members are like that in the film pack case arranged that the rear end of each guide member 31 is folded back on itself, in such a way, "that the Guide member is located between the front of the film unit, of which it forms a part, and the rear of the Cover sheet 64 (in the case of the foremost film unit) or the back of the in the direction of the front wall 48 and the Exposure opening 58 of next preceding film unit extends to the rear of the film unit. At his front At the end of 38, the guide member is folded over to the front and with the back of the front wall of the Housing next adjacent part, i.e. of the cover sheet 64 or the preceding film unit 10 connected to and attached to this attached near its rear end. Thus, the cover sheet 64 and successively the film units 10 are connected to one another by guide members 31, each of which extends from the rear Extend the end of a part to the front end of the next part to be removed from the film pack (film unit). The guide members 31 are arranged in a zigzag shape such that a stack of the cover sheet 64, a guide member 31, a film unit 10, another guide member 31, etc. results. The guide members 31 can each through perforations, Pre-cutting or the like. Be provided with predetermined tear points, such that the one with a film unit inside of the film pack connected and protruding from the film pack as a guide strip for removing this film unit of the guide member from the one attached to the preceding part, i.e. the cover sheet 64 or the preceding film unit 10 Section of the guide organ can be separated.

509 81 1/1030

According to the invention, the film pack 44 has means which come into engagement when a film unit is pulled out after the exposure with the exertion of compressive pressure, in order to tear open the container 11 and to empty its liquid contents between the layers 21a and 15 and as a thin layer to distribute between these layers. As shown in Figs. 8 and 9, this pressing device is in the form of a pressing device 70 integrally connected to the film packing box 46 at the front end thereof. The exercise device 70 is preferably made of a flat material such as sheet metal that is structurally rigid and strong as well as having sufficient flexibility to accommodate the varying thickness of a film unit as it is removed from the film pack. As can be seen, the device 70 has an overall parallelepiped shape with a front wall 72, a rear wall 74 and side walls 97, which each encompass the front ends of the front, rear and side walls of the container 46 to gain additional strength and rigidity and the pressure exerting device 70 on the Define the film pack box 46 as part of the film pack 44. The front wall 72 is provided with a rearwardly downwardly directed lip 96 and correspondingly the rear wall 74 is provided with a forwardly directed lip 78. The spreading device has a front end wall with a front section 80 and a rear section 82, which are separated from one another by a removal passage opening. The front part 80 and the rear part 82 of the front end wall are rolled over on themselves at their mutually facing edges, as a result of which cylinders or. Are formed of pressure bodies 90 and 92 which have a sufficient resistance to a bending apart or spread apart and act as a pair of pressure members.

509811/1030

The lips 96 and 78 are provided with snap flanges 86 and 88 at the front edges of the front wall 4 8 and the rear wall 56 of the film pack container 46 in engagement. The snap flanges 86 and 88 are inclined or tapered towards the leading edge of the film unit to facilitate the attachment of the To facilitate pressurizing device 70 on the film pack container; all that is needed for this is the pressure exerting device on the end face of the film pack container a slight deformation of the front and rear walls of the container and / or the pressure exerting device to be vardened in order to engage the lips 96 and 78 via the snap flanges 86 and 88 in the position shown in FIG to leave, in which the back of the front wall 82 rests against the end wall 54 deg of the film pack container.

As mentioned, as can be seen from the drawing, the minimum or compressed thickness of the film unit variable along the length of the film unit, such that the width of the gap or the outlet opening 84 between the pressure-exerting organs 90 and 92 should be variable such that these organs are independent of the change in the thickness of the film unit cause pressure to be exerted. To relative displacements of the preferably axparallel and coplanar To enable cylindrical pressure-exerting members, the rear part 82 is at the ends of the cylindrical pressure-exerting member 92 is provided with slots 94 in order to allow a relative movement of the pressure exertion member 92 relative to the member 90 to enable this towards or away from it.

In the embodiment described, it is indeed a zigzag shape shown folded arrangement of interconnected guide members and film units; Of course However, other devices or dimensions can also be used.

50981 1/1030

took to be provided to each -a film unit by'hand to be able to remove or remove from the film pack between the pressure exertion organs. Such devices are described, for example, in U.S. Patents 2,903,951, 2,909,977 and 2,946,270. There are others too Systems known to a guide member of a film unit when pulling out the preceding film unit or the cover sheet pull it out of the film pack to a position in which it can be grasped; such other Systems can be used in place of the system shown here.

The invention thus provides a simple, inexpensive film pack construction created, all of the parts required to produce multiple colored positive images or prints contains, and the production of these positive images or prints can be done in a simple, easy manner by one exposed film unit by hand from the film pack between a pair of pressure-exerting members, which are a are an integral part of the film pack, pulls out through it. The only other (external) structure becomes Generation of the colored positive prints only a recording exposure system, for example a lens, shutter, Viewfinder and the like is required with which the film pack is to be used. Each film unit forms an integral unit, which remains intact before, during and after recording, exposure and development treatment, such that the only manipulation is pulling out the film unit represents the emptying of the treatment liquid from a container into the film unit and the Distribution of this treatment liquid in the film unit and thus the generation of the dye transfer image

50981 1/1030

ensures while the film unit is outside of the film pack and outside of the camera if the film pack is in a Camera is included is located.

Each time a film unit 10 is removed, the one connected to the next following film unit Guide strip 31 advanced through the outlet opening 71 as far as is necessary to follow this film unit to be able to pull out the exposure exposure in the manner indicated above for the purpose of development treatment. If desired, the leader strip can be used on a case-by-case basis from the preceding and the following film unit after the Removal of the film unit concerned from the camera.

In the. preferred embodiment of the invention is the front end portion 38 of the guide sheet 31 on one of the two main surfaces of the rear end portion of the respective attached to the preceding elements, provided that when attached to the exposure surface by its The position or composition does not interfere with the exposure of the unit. However, the front portion 38 of the leader sheet 31 can be attached to the preceding element, i.e., the preceding Film unit or the dark cover slide, on the surface opposite the receiving opening one may be attached in front of the rear end of the element concerned, provided that the length of the guide strip is sufficient to allow it to be gripped through protrude the removal opening, further provided that the guide strip is pretensioned against one another for its removal from the cassette including the passage from the Pressure exertion organs required slipping capacity, for example by its composition or by a

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2U1751

has coating, and further provided that the guide strip in a simple manner outside the camera of the previous element and within the reach of the User is disconnected.

As material for the dark cover slide and the guide strips any conventional paper and / or polymer material comes, for example as described above, question that is flexible enough to accommodate the To be able to perform guide strips described function, the material in question can be opaque, translucent or be transparent, as required; it may optionally be provided that it is either separated from the film unit after the development treatment, for example with or without simultaneous separation of the tearable container; alternatively it can also be provided that it is on a Surface of the film unit, in the case of transparent material, for example on the viewing surface, preferably for aesthetic reasons with the same area as the film unit, using any suitable adhesive, which can be provided on the intended contact surface, is glued. In cases where the guide strip remains on the development-treated film unit, the decorative aspects of the leader, i.e., its Color, its structure and its shape depending on the desired visual appearance can be selected.

The invention has been described above on the basis of preferred exemplary embodiments, which are modified in detail can, however, without thereby departing from the scope of the invention will.

Patent claims:

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Claims (1)

Patent claims: IyI composite film unit for diffusion transfer photographic process, which in a layer on a dimensionally stable support at least one light-sensitive. Silver halide layer, the one for dye imaging after the diffusion transfer process suitable dye material (color former) is assigned, as well as · a dyeable layer (image receiving layer) for taking up νοηΊη this layer diffusing color former from the light-sensitive silver halide emulsion layer (s) has associated color former layer (s), characterized in that the film unit forming layer (10) on that of the dyeable image-receiving layer (21) opposite side of the photosensitive silver halide emulsion layer (s) (15 to 19) for a development treatment composition (12) used in the diffusion transfer process, permeable for however, the dye material used for dye image formation by the diffusion transfer process is impermeable Has barrier layer (25). 2. Composite film unit according to claim 1 for the photographiscne Diffusion transfer process, characterized in that it contains the following components: A first dimensionally stable transparent layer (24-b); a dyeable layer (image receiving layer) (21) for receiving a dye image diffusing into it the diffusion transfer process producing dye material (color former) j an opaque layer (20); a light sensitive Silver halide layer (15, 17, 19) which is used for dye image formation by the diffusion transfer process suitable dye material (color former) added 509811/1 030 -. 69 ~ is arranged; a development treatment composition used in the diffusion transfer process (12) transmissive for diffusion transfer imaging serving dye material, however impermeable barrier layer (25); a second dimensionally stable transparent layer (24a); Means (ll) for bringing in a development treatment composition (12) for the diffusion transfer process between the second dimensionally stable transparent layer (24a) and for the image-forming Paraffin material impermeable layer (25); as well as means (26) for maintaining the composite Film unit as an integral unit after diffusion transfer development treatment. 1 or ' 3. Film unit according to ClaimY2, characterized in that it is marked. treatment net that the development / composition (12) a. ■ first development treatment pH and that the Film unit has means (23b, 23a), after the substantial formation of the dye transfer image in the two dyeable image-receiving layers (21b, 21a), the state of To change the treatment composition from the first development treatment pH to a second pH, which increased the two dye transfer images Have stability. 4. A film unit according to claim 3, characterized in that the first development treatment pH is in the alkaline area and that the second pH value is lower. than the first is. 50981 1/1030 5. Film unit according to claim 4, characterized in that the second pH value by more than one pH unit is below the first pH. 6. Film unit according to one or more of claims 3 to 5 »characterized in that the means for converting the treatment composition from the state with the first pH value to the state with the second pH value after the essential dye transfer image generation in de. ' a dyeable image-receiving layer (23) polymeric neutralization layer (23b) at least between the first dimensionally stable transparent layer (24b) and the image receiving layer (21) or the second dimensionally stable transparent layer (24a) and the layer (25) impermeable to the dye image-forming material. 7. Film unit according to one or more of the preceding claims, characterized in that they have means for introducing or generating an opacification 'or Opacifier between the second dimensionally stable layer ^ ^ next adjacent light-sensitive silver halide layer (15) in such an amount that a (post) exposure of the light-sensitive silver halide layer (s) (15 to 19) during the development treatment of the film unit (10) in the presence of the second dimensionally stable transparent Layer (24a) more conspicuous, for the photosensitive layer actinic radiation is prevented, and that the opaque Layer (20) a (post) exposure of the photosensitive layer (s) (15 to 19) during the development treatment of the film unit in the presence of on the first dimensionally stable layer (24b) which is conspicuous and prevents actinic radiation for the light-sensitive layer. 8. Film unit according to one or more of the preceding claims, characterized in that the opaque layer (20) reflects actinic radiation. 50981 1/1030 9. Film unit according to claim 8, characterized in that that the opaque layer (20) is a dispersion of titanium dioxide in one for the developing composition Contains permeable polymeric binder. 10. Film unit according to claim 8 or 9, characterized in that the opaque layer (20) made of, multilayered and a / a ^ "dispersion of Carbon black in a polymeric binder permeable to the treatment composition between the opaque one Titanium dioxide layer and .the next adjacent silver halide layer (19). 11. Film unit according to one or more of the preceding claims, characterized in that the opacifying or opacifying agent actinic radiation ' absorbed. 12. Film unit according to claim 11, characterized in that that the opacifying or opacifying agent contains an inorganic pigment. "·. 13 · Film unit according to claim 12, characterized in that it is e k e η η ζ e i c h net that this is an inorganic reflective pigment having opacifying or opacifying agents is contained in the treatment composition (12). 509811/1030 2U1751 14. Pilm unit according to one or more of the preceding claims, characterized in that the means for introducing the treatment composition one having rupturable containers (11) containing the treatment composition (12) along one edge of the pilm unit (10), from which when a compressive pressure is exerted on the container the treatment composition contained therein (12) between the second dimensionally stable transparent layer (24a) and that for the image-forming layer. Dye material impermeable barrier layer (25) is emptied and distributed, 15 pilm unit according to one or more of the preceding claims, characterized in that that for dye image formation by the diffusion transfer process suitable material is a dye developer for silver halide. 50981 1/1030 16i film unit according to claim 15, characterized net that the dye serving as a color former contributes soluble and diffusible at a first pH, and essentially nondiffusible at a second pH. 17. Film unit according to one or more of the preceding claims, characterized in that the layer (10) forming the film unit between the opaque ' Layer (20) and that for the dye image-forming material are at least two selectively has sensitized silver halide layers (15, 17, 19), each of which has a predetermined one for the formation of a dye image Color as a function of the exposure exposure of the silver halide layer concerned (Color former) is assigned. 18% .Film unit according to claim 17, characterized in that each of the selectively sensitized Silver halide layers (15, 17, 19) of the film unit have a predominant spectral sensitivity, each for separate Has spectral ranges and that the dye image-forming agents assigned to the individual silver halide layers Substances (color formers) after the development treatment are essentially complementary to the predominant sensitivity range of their associated silver halide layer Have spectral absorption range. . Film unit according to claim 18, characterized in that the treatment composition (12) and the film unit forming laminate (10) has pH converting means for the treatment composition the substantial diffusion of the dye image-forming substances (color formers) into the receiving layer of a first alkaline development treatment pH to one has a second pH value below this first pH value, at which the dye produced by the color formers Transmission image has increased stability. 50981 1/1030 20. Film unit according to one or more of the preceding claims, characterized in that the selectively sensitized silver halide layers as essential layers, a red sensitized silver halide emulsion layer (19), which is one for dye image formation by the diffusion transfer method appropriate cyan dye is assigned, a green sensitized silver halide emulsion layer (17), which a magenta dye suitable for diffusion transfer dye image formation and a blue sensitized silver halide emulsion layer. (15) which is one for dye image formation by the diffusion transfer method appropriate yellow dye is assigned. 21 · Film unit according to one or more of the preceding claims, in particular according to claim 1. characterized in that the said development treatment composition (12) permeable, but impermeable to the imaging dye material barrier layer (25) made of butyl acrylate / diacetone acrylamide / styrene / methacrylic acid there is a ratio of 60/30/4/6. 22. Process for generating dye images according to the Diffusion transfer photographic processes using a film unit of one or more of the preceding claims, in particular the film unit according to claim 1, characterized by the following procedural steps: (a) Exposing the photosensitive laminate forming the film units to incident actinic radiation (b) Contacting the transparent to the dimensionally stable Carrier (24a) facing surface of the fUi the image generating Dye material impermeable barrier layer (25) having a Treating composition (12) and developing exposed silver halide layer (s) (15 to 19) for 509811/1030 Formation of an image-wise distribution of moveable Dye image-forming material (color former) as Function of the point-wise extent of the photo-exposure of the silver halide layer (s) I (c) Diffusion transfer of at least part of the image ■ have distribution of the mobile dye image-forming; Materials (color former) in the for receiving the one [ diffusing color former suitable dyeable "or image-receiving layer (21) for producing a dye image * that in the dyeable image-receiving layer, depending on the imagewise distribution of the color former. . Method according to claim 22, characterized in that that the pH level in the film unit after the substantial dye image formation in the two dyeable Image-receiving layers of a first development treatment pH adjusted by the treatment composition changed to a second pH value at which the dye image has increased stability. . Method according to claim 23, characterized in that that as a dye image-forming material (color former) a dye is used which is a silver halide developer and contributes to the composition of the treatment is soluble and diffusible at the first pH as a function of photo exposure of the film unit and at the second pH is essentially nondiffusible. . A method according to claim 23 or 2 ^, characterized in that the first or development treatment pH is in the alkaline range and that the second pH value is more than one pH unit below the first "pH value. 509811/103 0 26. The method according to one or more of claims 22 to 25 *, characterized in that in Coverage with the surface of the silver halide layer facing the dimensionally stable transparent carrier layer (en) (15) introduces or generates an opacifying agent. 27. The method of claim 26 using a composite Film unit according to several of the claims ·· 1 to 21, which has the following components: a sequence of layers with a first dimensionally stable, transparent for incident actinic radiation Layer; a dyeable image receiving layer; an opaque layer; at least two selectively sensitized Silver halide emulsion layers which have predominant spectral sensitivity for separated Have regions of the visible electromagnetic spectrum and each of which has an imaging dye material is assigned, which provides a dye which, after the development treatment, becomes one of the predominant Sensitivity range of the associated silver halide emulsion layer (en) has substantially complementary spectral absorption range, one for the treatment composition a permeable, but impermeable to dye imaging material barrier layer (25); a second dimensionally stable layer which is transparent to incident actinic radiation; Means of cohesion the layers in a substantially fixed mutual arrangement; furthermore a tearable container for the alkaline developing treatment composition which is in substantially uniform dispersion Contains opacifying agent in sufficient quantity to be used after the alkaline treatment composition has been distributed with the first pH as a layer between the second dimensionally stable transparent layer 50981 1/1030 and the next adjacent selectively sensitized silver halide emulsion layer incident actinic exposure radiation does not substantially affect the silver halide emulsion layers can pass through, the tearable container along an edge of the photosensitive element is arranged so that the alkaline treatment composition contained in the container between the second dimensionally stable transparent layer and the layer which is impermeable to the image-forming dye material can be introduced, characterized in that (a) that the photosensitive laminate of the film unit (10) is exposed to incident actinic radiation (Fig. 2,3), (b) that the alkaline treatment composition (12) from the container (II) between the second dimensionally stable clear layer (24a) and the layer (25) which is impermeable to the dye image-forming material is emptied (Figures 4, 5) (c) that the individual selectively sensitized silver halide emulsions develop in this way (d) imagewise forming distributions of mobile dye as a function of development (e) that by diffusion at least part of the imagewise distributions of mobile dye in the dyeable image-receiving layer to form a dye image transfers according to the imagewise dye distributions - (f) that the composite film unit after the developing treatment-as one-piece unit maintains (Figures 6 and 7, -) ·. "..-._ 28. The method according to claim 27, using a film unit which has the following components: a laminate of the following essential layers in the specified order: a first dimensionally stable, transparent layer impermeable to alkaline solution; one off 509811/1030 2U1751 alkaline solution dyeable polymeric image-receiving layer; an inorganic light-reflecting pigment layer containing titanium dioxide which is permeable to alkaline solution; an opaque layer containing carbon black which is permeable to alkaline solution; a red-sensitive silver halide emulsion layer having an associated cyan dye; a green-sensitive silver halide emulsion layer having an associated magenta dye; a blue-sensitive silver halide emulsion layer having an associated yellow dye, the cyan, magenta and yellow dyes, respectively, being silver halide like and soluble and diffusible in an alkaline medium at a first pH; a polymeric barrier layer which is permeable to alkaline solution but impermeable to imaging dye; a second, dimensionally stable _T transparent layer impermeable to alkaline solution; a polymer layer disposed between at least one of the dimensionally stable transparent layers and the next adjacent layers thereof, which polymer layer has sufficient acid capacity to lower the pH of the treatment composition from the first pH at which the cyan, magenta and yellow dyes are soluble and are diffusible, to be reduced to a second pH value at which the said dyes are essentially non-diffusible, as well as means for fixing these layers of the laminate in their mutual position; furthermore a rupturable container with an aqueous alkaline development treatment composition having the first pH value, in which an opacifying agent is contained in uniform distribution, which is essentially non-diffusible from the treatment composition and is present in a sufficient amount to permit the erfeen after distribution of the pH-value aqueous alkaline treatment composition as a layer between the second dimensional • A 509811/1030 stable clear layer and for the image dye impervious barrier layer means a layer having an optical transmission density greater than about 6 density units with respect to incident actinic radiation for the silver halide emulsion layers, and wherein the container is fixedly arranged along a leading edge of the photosensitive element such that the in the container contained, the first pH having aqueous alkaline treatment composition by Aus. exerting compressive pressure on the container in the one-way direction between the second dimensionally stable clear Layer and the barrier layer impermeable to the image dye can be emptied, thereby g e k e η η ζ e i without t, (a) exposing the film unit to incident actinic radiation (b) applying a compressive force to the frangible container exerts to dispose of the aqueous alkaline treatment composition in the container between the second dimensionally stable clear layer and the barrier layer impervious to the image dye (c) that here we have the red-, green- and blue-sensitive Can develop silver halide emulsions (d) that the cyan, magenta and yellow dyes as a result of the development of their associated silver halide emulsion to be immobilized (e) thereby providing an imagewise distribution of cyan, magenta and yellow mobile dyes as a function of point-by-point Extent of exposure of their associated silver halide emulsion is formed (f) undergoing at least a portion of the imagewise distribution of cyan, magenta and yellow mobile dyes Diffusion onto the polymeric image-receiving layer which is permeable to alkaline solution and can be dyed with the dyes 509811/1030 transfers in order to give it a multicolored pigment image produce (g) that after substantial dye transfer one sufficiently large proportion of the ions of the aqueous alkaline treatment composition by diffusion into the polymer acid layer transfers to the alkalinity of the film unit from the first, above the pKa of the pH sensitive dyes lying first pH value at which the cyan, magenta and yellow picture dyes are soluble and diffusible on to reduce a second value at which the cyan, magenta and yellow image dyes are essentially non-diffusible are (h) that the composite laminate structure .after the development treatment maintained as an undivided unit. 50981 1/1 030