DE2340944A1 - UNITARY LIGHT-SENSITIVE ELEMENT AND ITS USE IN A COLOR DIFFUSION TRANSFER PROCESS - Google Patents

Description

dr. W.Schalk dipl.-ing. P. Wirth dipl.-ing. G. Dannenberg DR.V. SCHMIED-KOWARZIK · DR. P. WEl N HOLD · DR. D. GUDEL

6 FRANKFURTAM MAIN

OR. ESCHENHEIMER STRASSE S9

FDN-369
Dr.H / bgr

^G AP Corporation

New York, N.Y., 10020 / USA

Unitary photosensitive element and its use in a color diffusion transfer process

The present invention relates to a unitary photosensitive member and its use in a color diffusion transfer process; it "particularly relates to a color diffusion transfer process for generating positive colored transfer images on a pickling receiving layer, which faithfully reproduce the hue, saturation and density changes of the original.

This process uses photosensitive negative packaging (light-sensitive material) blue, green and red sensitized Silver halide emulsions used in gelatin or similar colloid layers, each of which is one immediately adjacent nucleating colloid layer producing the opposite color and each of the nucleating colloid layers Colloid counter-layers to the other photosensitive layers by a distance of at least 3 to 6 Micron. Is separated. This separation is brought about by

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passing an appropriate number of inert gelatin layers, each 3 to 6 microns thick. The photosensitive Layers contain the above-mentioned silver halide emulsions with known sensitizing dyes sensitized for the appropriate primary color range are. For negative development with a p-phenylenediamine developer are the light-sensitive parts (layers) preferably of 2 layers, one of which is the silver halide emulsion in gelatin or the like Colloid together with a cleaner for the oxidized p-phenylenediamine, for example a non-diffusing one Color formers of a hue-producing substance (these color formers are known) contains, and the other, very thin (less than 1 micron) thick layer of an inert gel and between the silver halide emulsion in Gelatin or a similar colloid layer and the nucleating colloid counter layer (companion layer) arranged is. This preferred embodiment has the advantage that both the oxidized product of p-phenylenediamine in the negative development is limited to the development layer, as well as that thereby the developability of the p-phenylenediamine developer is increased.

Each of the nucleating colloid layers associated with the blue-, green- and red-sensitized layers, respectively, is provided with a divalent (two-equivalent) _i colorless, non-diffusing coupler capable of reacting with the one described in the to react the remaining positive silver halide image in the adjacent layer and to convert this alone into a soluble, diffusible positive color image with a color complementary to the hue of the light recorded in the negative recording: namely yellow, which is associated with the blue-sensitive silver halide layer, magenta (purple red),

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associated with the green-sensitive silver halide layer and cyan (blue-green), that with the red-sensitive silver halide layer is associated. The divalent (two-equivalent), colorless, non-diffusing couplers react in particular with the oxidized color developer (of the p-phenylenediamine type), which in turn in the physical Development is formed at the colloidal dispersions of precious metals or their sulphides (preferably colloidal silver one suitable for its simultaneous use as a yellow filter during exposure Size (e.g. Carey-Lea-Silver)), a the system during the Transfer of saturating p-phenylenediamine developer and undeveloped silver halide from the neighboring one Layer are involved, which contains the positive remainder of the negative development.

These divalent couplers have the general formula

X-C-L-B

X = -SO ₃ H, -COOH or H;

C is a central coupler structure of a type capable of interlocking with an oxidized p-phenylenediamine molecule of the Y-CD type, in which Y has the same meaning as X, to a soluble azomethine or indoaniline dye form,

L is a radical from the group consisting of the oxy, azo, azoxy, alkylidene, sulfoxy, carboxy or other radicals of who are known to undergo "decoupling reactions" which involve the conversion of the coupling molecule into do not prevent a colored dye, and B mean a ballast group which the molecule in a makes swollen gelatin matrix non-diffusing.

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The initially non-diffusing colorless coupler should converted into a cyan, magenta or yellow dye by the color-forming reaction, depending on the layer in question simultaneously with the color formation, the colored product in the swollen gelatin matrix is solubilized and made diffusible. These Solubilization and diffusibility can be after a be effected by three different mechanisms:

1.) X = -SQ..H, Y = H: With this mechanism, the hydrophilic nature of the coupler core molecules due to the hydrophobic nature introduced by the ballast group more than balanced. In the formation of a dye by coupling with the color developer where Y = H, the Ballast group, whereby the originally hydrophilic group X = -SO_K or -COOH in a clear preponderance is brought.

2.) X = -SO, H or -COOH, Y = -SO _n K or -COOH: This mechanism is similar to the above mechanism with the exception that the originally hydrophilic nature achieves a re-reinforced clear preponderance, which is reinforced at least twice by the additional coupling of a hydrophilic residue,

3.) X = H, Y = -SO ₃ K or -COOHi In this mechanism, the originally non-diffusing colorless coupler has no hydrophilic nature and the hydrophilic nature of the dye formed comes from the solubilizing developer via the oxidative coupling.

In all three cases the ballast group is split off and left behind in the coupling reaction. The use of the dye solubilizing developers in which

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γ = SO-H or -COOH is a new type in a dye transfer system to generate a diffusivity. In addition, these developers have improved developer resistance and penetration during development, which is an additional advantage over the known systems in which Y = H.

The preferred combination is that of Mechanism No. 3, wherein the originally non-diffusing colorless coupler does not have a hydrophilic group which makes it difficult to be soluble in high-boiling solvents, so that it can be dispersed in the layer as a dispersion in such high-boiling solvent wherein there is a sharp distinction between the unreacted lipophilic coupler and the matrix-soluble and diffusible hydrophilic product of the color-forming reaction ". This greatly simplifies the control between diffusing and non-diffusing states. To support this case, the ballast group consists of a straight or branched aliphatic hydrocarbon chain having from 5 to 30 carbon atoms or any other radical which functions in this way, such as is known, for example, from US Pat. No. 3,408 194. Except for the above In the stated advantage, the couplers in which X = H and the other couplers in which X = —SO ₃ H or —COOK have the advantages in common that they are colorless before the oxidative coupling, so that they reduce the transparency of the others Parts other than the silver halide parts of the photosensitive package do not interfere with exposure to actinic light; however, in the stages described below, they provide a fully formed dye upon transfer to the receiving sheet. The connections generally described

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and reactions are found in U.S. Patent 3,227,531, but are not described in that a response-assisted intranegative transmission according to the invention as defined below, used.

Examples of p-phenylenediamine type solubilizing developers, those with the preferred cyan, magenta and yellow color-forming, colorless, non-diffusing Couplers to be used are the following:

CH ₃ -N-CH ₂ CH ₂ SO ₃ H

C ₂ H ₅ -NC ₃ H ₅

SO ₃ H

III

IV.

NH ₂

If

COOH

HN-C-CH ₉ CH ₉ -COOH

COOH

VI.

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CH ₃ CH ₂ -N-CH ₂ CH ₂ SO ₃

CH-

The divalent, non-diffusing coupler works with such an oxidized p-phenylenediamine developer, formed by the reaction, including the nuclei and undeveloped silver halide, the originates only from the adjacent photosensitive layer, with formation and release for solubilization and Diffusion of a soluble, diffusible dye a color complementary to the color of the light recorded as the negative record. With this mechanism the dye does not diffuse out of the silver halide layer, but only into that layer from the nucleating layer Districts adjacent to the undeveloped silver halide-containing districts. This dye transfer mechanism is due to a specific intranegative transfer of this residual silver halide only introduced to the adjacent nucleating layer. This intranegative transmission is partly due to the addition (after or simultaneously with the development of the negative recording by the p-phenylenediamine developer or any other suitable developer or developer combination) critically low concentrations of a silver halide solvent such as sodium thiosulphate, (less than 1-0 g / l, preferably less than 2 g / l) or in concentrations that depend on the solvent effect Sodium thiocyanate or any other equivalent silver solvent is introduced.

The present invention is not to be confused with the known methods, as for example in the US Pat. No. 2,352,015, in which silver halide remaining in a layer for release of a dye or a color-forming substance is to be used in an adjacent layer which is passed through

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a silver halide solvent concentration is introduced which is more likely than a non-specific overall transfer initiates a partial transfer of soluble ions to the adjacent color-forming layer. With the ones used so far Silver halide solvent concentrations (U.S. Patents 2,352,015, 2,673,800, 3,244,001, 3,443,940, and the like) becomes the silver halide for the eventual transfer of silver ions to any other color-forming layer sufficiently solubilized, being in addition to the correct positive Recording of a given silver halide image received ghost images (shadow images) of an incorrect color tone will. This disadvantage is known and is described, for example, in US Pat. No. 2,673,800, in the cumbersome and complicated methods and devices are used to obviate this disadvantage. This awkward and complicated devices and measures are avoided by the present invention.

Silver halide solvent concentrations are used in accordance with the present invention used, which themselves are not sufficient to cause sufficient solubilization and which also not sufficient to initiate the known transport mechanisms. The invention is explained in more detail below,

It was not to be foreseen without further ado that small concentrations of silver halide, which had to be considered to be too weak containing (less than 10 g / l, preferably below 2 g / l) would be enough _t to silver halide in a significant rate of the silver ions transfer from the silver halide Solubilize out layer. It has surprisingly been found that when an immediately adjacent layer (with a distance of 0 to 1.0 microns) has a reaction for the silver ion, for example a silver reduction,

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initiating substance contains the concentration of the silver halide solvent now for a substantial mass transfer of silver ions between this layer and of the reacting layer over the 0 to 1 micron limit now enough. It was also found that this effect decreases sharply with increasing distance, so that then, when the reaction causing layer is further away (3 to 6 microns away), the critically low concentration works again as expected on silver solvent, i.e. insufficient solubilization for a considerable Transfer of silver ions from the silver-supplying substance to a more distant, reaction-causing layer, results and no useful diffusion is achieved.

This is best understood by looking at thermodynamics Concept of chemical potential reminds that for the entropy force fields is the same as the "electromotive" Force for the electric force fields; likewise the mass transfer (i.e. the silver ion transfer) for the entropy force fields the same as the current or the movement of electrons for the electric force fields. From this it can be seen that the critically low concentration of silver halide solvent used is not itself not Concentration gradient profile (according to a "shock" mechanism) results, which is sufficient for the build-up of a chemical potential between adjacent layers, which for the significant transfer of silver ions from one layer to the other is large enough. This also shows that the the layer which provides the reaction itself because of its ability to act as a sink point * for silver ions ("pulling mechanism") work, cannot result in a concentration profile gradient, which is sufficient to build up a chemical potential between adjacent layers that is sufficient for significant silver ion transfer is big enough between layers.

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The sum of their capacities ("push-pull" mechanism) is sufficient however, from generating a concentration profile gradient between adjacent layers that is large enough is for significant silver ion transfer. It also shows that even their total capacities ("the push-pull mechanism") to initiate silver ion transfer between the silver source and beyond (3 to 6 microns) removed silver reactive layers are insufficient for significant silver ion transfer.

The above "thermodynamic argument explains the Difference between the solvent-induced silver ion transfer according to the known systems and reaction-assisted silver ion transfer according to the system of the invention. The former is characterized by high silver solvent concentrations, which are sufficient to move the silver halide through the entire system without taking into account the intended reaction centers, which leads to the formation of Ghosting (silhouettes). The latter is characterized by sufficiently low solvent concentrations, to provide the sinking potential * of the reaction center, which plays an essential role in mass transfer of silver ions, with the neighboring reaction centers having a significantly greater effect than those more distant. With this kind of intranegative transfer it is possible to transfer silver ions on restrict the desired intranegative transmissions without adding undesirable intranegative transmissions in To have to buy. Although these two modes of transmission were known, it is by fortunate coincidence managed to cross the dividing line between the two. This crossing line had to go through experimen-'Csink potential)

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Partial changes in the concentration and distance parameters for the investigated systems are found, with the related experiments are described in more detail in the following exemplary embodiments.

In general, the parameters that the Define response supported transmission mode for a given system and silver solvent, not independently from each other and such transmission mode is not a function of any of them. For example, although a low silver solvent concentration of 2 g / l for the low values used in the invention It can be characteristic that an excessively thin separating layer between the silver source and the undesired reaction center can have the effect of undesired transfer is initiated. For example, if a spacer layer with a thickness of 3 to 6 microns according to of the invention with too high a concentration of silver Ιο solution is combined, the undesired transmission mode is activated even if the distance parameter is within of the frame according to the invention lies. B. In the practical implementation, the distance parameter is determined and the silver solvent concentration is found to be below the dividing line between these two types of transfers lies. This value is of course different for different silver solvents.

It is within the scope of the present invention that when the photosensitive negative pack is made is, taking into account the distance parameters given above, taking care that the critically low Silver solvent concentration not exceeded

en becomes 'the intranegative transfer' to the following three.

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are limited without the need for complicated facilities to prevent the other undesirable intranegatives Transfers required: The undeveloped silver halide of the blue record becomes specific and transferred only to the adjoining layer providing the reaction, which has a diffusible positive Yellow image supplies; the undeveloped halide from the green record is specific and unique to that adjacent, the reaction causing layer transferred with the formation of a diffusible positive magenta · image; and the undeveloped silver halide from the red record becomes specific and unique to the Adjacent or bordering, a reaction-resulting layer transferred, which is a diffusible, positive Cyan image supplies. The overall effect of the only three intranegative silver transfers is a compound one Dye transfer to a shaking receiver sheet that the change in hue, saturation and density of the original (s) in a realistic manner reproduces. The invention will be elucidated with reference to the examples below and the accompanying one Drawings explained in more detail. Show:

1 shows the exposure of the new negative 3-color pack according to the invention before the stepwise development with a color developer and a silver halide solvent,

Fig. 2 shows the state of the negative packing according to Tig. 1 after exposure and negative development, which only shows the three intranegative silver transfers;

3 shows the negative packing according to FIG. 2 during the transfer of dye from the negative packing

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the pickling receipt sheet;

4 shows the reproduction of the original scene on the receiving sheet;

Figure 5 is a schematic representation of a developing chamber and developing rollers useful in a camera with explanatory labels indicating the contacting negative material with the receiving sheet.

Fig. 6 shows another embodiment of the development chamber and rollers for the same purposes as in fig Embodiment according to FIG. 5;

Fig. 7 shows a permanently bound element, which. From the negative photosensitive material, a receiver sheet and a developer container, which is in a laterally reversed corrected camera is used and the completion of the development allowed outside the perimeter of the camera;

Figure 8 shows the same element after exposure and development;

Fig. 9 shows a permanently bonded element consisting of the negative photosensitive material, a receiver sheet and a developer container, the can be used in a camera with conventional optics without lateral reversal correction should and allows the completion of the development outside the confines of the camera;

Figure 10 is a summary of the photochemical reactions

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and explanation of the symbols used in the photosensitive Elements of Figures 1 to 4 appear.

Each of FIGS. 1 to 4 inclusive has lettering indicating the chemical occurring in each of the layers Explain the reaction and it has symbols used to denote chemical reagents. The features of the drawings are explained in more detail below.

The photosensitive negative pack is placed on a. Carrier pad 1 applied, which is either a film base, such as a polyester or thermoplastic Cellulose film backing material, or around a baryta-coated paper backing or one with polyethylene Laminated paper backing can be used for the application of the silver halide gelatin or colloid layer has been subjected to a surface treatment known per se to improve adhesion (subbing).

Layer 2 is a gelatin or gelatin replacement matrix, the development nuclei in which it is colloidal particles of precious metals or precious metal sulfides, and a bivalent (two-equivalent), Contains non-diffusing coupler which is capable of the mechanism described above is to form a cyan dye for solubilization and diffusion in the alkaline swollen matrix. The divalent, non-diffusing coupler is preferably in a high boiling point organic solvent or plasticizer dispersed to form small droplets that are uniform within the matrix of layer 2 are distributed.

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Layer 3 is 0.5 to 1.0 Micron thick gelatin or gelatin replacement matrix / their The main task is to prevent the transfer of the oxidized developer from the layer 4 to thereby to effectively protect the barrier layer (sealing layer) 2 against this transmission. For this purpose, the Layer 3 contain known hydroquinone derivatives that act as antioxidants for reaction with a migratory oxidized developer, which may hit the layer 3 under extreme conditions, can be used.

Layer 4 is a light-sensitive silver halide layer which is sensitized to red light and which contains a sufficient amount of a conventional, non-diffusing color developer, the sole purpose of which, according to the invention, is to remove all of the completely exposed areas of this layer remove oxidized color developer. Layer 5 is a gelatin or gelatin replacement layer with a thickness of 3 to 6 microns, the purpose of which is to keep the spacing parameters within the scope of the present invention. The layer 6 has the same function and composition as the layer 2, but the divalent, non-diffusing cyan coupler is replaced by a divalent, non-diffusing magenta coupler. Layer 7 has the same function and composition as layer 3 and seals layer 6 against any undesirable migration of the oxidizing developer out of the layer. Layer 8 is a photosensitive silver halide layer like layer 4, but which is sensitized for green recording. Layer 9 is identical to layer 5 in terms of its composition and function and serves to maintain the

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Stand parameters within the scope of the present invention.

The layer 10 has the same function and composition as the layer 2, but this time the divalent, non-diffusing cyan coupler through a bivalent, non-diffusing yellow coupler is replaced. This layer also contributes to the filter protection of the photosensitive layers 4 and 8 against blue light during exposure at. The layer 11 has the same function and composition like layer 3 and seals layer 10 against any disturbing migration of the oxidized developer out of layer 12. Layer 12 is is a photosensitive silver halide layer like layer 2, but this time the silver halide not optically sensitized and therefore only sensitive to blue light. The layer 13 is around a gelatin or gelatin replacement matrix layer that serves to physically protect the negative packing.

In FIG. 2, the receiving sheet on a white opaque base 17, for example a pigmented with titanium oxide film base or a _t baryta-coated paper pad or a laminated with polyethylene paper backing applied which has been prepared for oils coating for a surface treatment process (subbing process) is. Layer 16 is a gelatin or gelatin replacement layer containing encapsulated organic acids or non-diffusing organic acids. Contains acids in concentrations high enough to neutralize the alkali spread from the developer container in the form of a layer 14. The layer 14 spreads from the developer container between the acidic layer 15, which contains a hydrophilic matrix material that can acidic dyes, and the protective

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surface 13 of the negative material. The developer solution contains enough alkali and buffer to last for the duration. of the transfer process to maintain a pH greater than 10.3, and it contains enough solubilizing color developer and adjuvant to develop the light struck areas, and it works in conjunction with the divalent, non-diffusing couplers and the critically low concentration of silver solvent (below 10 g / l, preferably below 2 g / l) within the teachings of the present invention. The liquid layer 14 also contains sufficient water to penetrate all layers 2 to 13 in the negative material and layers 15 to 16 in the receiver sheet and cause them to swell. In addition to these other components, the developer composition can also contain substances which increase viscosity, for example thickeners such as methyl cellulose, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone and the like. _t

In Fig. 1, the negative pack is shown before development and during exposure. By labeling the conversion of the above-mentioned original into the correct latent image recording is indicated. The for the Sensitizers used in silver halide layers (4, 8, 12) are known per se. With the red-sensitizing In general, dyes are meso-substituted Carbocyanines and those dyes that sensitize in the J band. These include selenthiomethylethylcarbocyanines. The green-sensitizing dyes are preferably of the pseudocyanine type, which give excellent results. Other green sensitizers are those. Oxacarbo cyanine dyes and Combinations of these oxacarbocyanine dyes already have been used with success.

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After the three records are appropriately recorded Fig. 2 and the corresponding parts of the lettering show the effect of development initiation and the only three intranegative silver ion transfers. The negative development takes place with the oxidized p-phenylenediamine from this stage either by reaction with the non-diffusing coupler in layers 4, 8 and 12, removed with the antioxidant in layers 3, 7 and 11 or due to its own half-life will. The soluble developer forms a nondifference in this reactive detergent or remover founding dye because the ballast group does not uncouple. The undeveloped silver halide that the positive recording of the respective layers 4, 8 and 12 is represented by only three intranegative transfers transferred to the correct layers 2, 6 and 10 just to initiate a transfer process, as shown schematically and is represented by the lettering in FIG. 3.

The bivalent, non-diffusing Küppier are through Labeling indicated in layers 10, 6 and 2 and they can be couplers known per se, as described, for example, in U.S. Patent 3,227,551; in particular those in those in the above general formula X = H, those with the solubilizing developers with Y = -SO-H or -COOH work together as indicated in the discussion. These couplers are preferably in a high boiling solvent dispersed.

Subsequent to the transfer of the composite dye Bildes in Fig. 3 is the receiving sheet from the negative package peeled off, the high alkalinity in the caustic layer being neutralized by layer 16. On the

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Receiving sheet (see Fig. 4) is a realistic one Figure of the original (see. Fig. 1) to be recognized.

example 1

OCH ₃

OHO

> · J! J

(CH ₃ ) ₃ CCCC-NH-0

C ₁₈ H _3n -N-CH ₃

A photosensitive element was prepared having the following layers:

1. film base;

2. The above yellow _t divalent (two-equivalent) _f non-diffusing. Coupler was dispersed in a high boiling solvent such as tricresyl phosphate in a gelatin matrix containing Carey Lea colloidal silver.

2 The coating weight of the yellow color coupler was 1.0 g / m 2;

3. A very thin (0.4 micron) layer of gelatin that contained 2,5-di-teit-amylhydroquinone as an antioxidant; -

4. A non-sensitized bromide iodide emulsion which

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the usual coupler 1- (2,4,6-trichlorophenyl) -3-3- [a- (2,4-di-tert-amy%) henoxyacetamide] benzamide-5-oxo-2-pyrazoline contained. The silver halide emulsion was applied at a coating weight of 1.0 g silver / m. Of the common couplers were half the coating weight.

A weighting film was provided with the following layers:

1. One under the trade name PRINTON® in stores available opaque film backing which is a titanium oxide pigmented cellulose acetate film backing material acted;

2. A layer of acid treated gelatin in a Layer thickness of 10.0 microns was applied.

The photosensitive member was passed through a continuous graduated gray wedge exposed and in intimate connection with the receiving sheet with a developer solution as in Fig. specified treated. The developer solution had the following composition, based on 1 1 solution:

Developer VI 5.0 g Phenidone B 0.125 g Metol 0.125 g Sodium thiosulfate 1/0 g Sodium sulfite 4.0 g Benzyl alcohol 4.0 ml KOH 21.0 g Boric acid 18.0 g Hydroxylamine sulfate 2.0 g Nitrilotriacetic acid (sodium salt) 4.0 g Sodium chloride 2.5 g Alipal® CO-436 ⁺ * 0.83 ml

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Methocel® ⁺⁺⁾ 1.0 g

Trade name for the ammonium salt of a sulfonated nonylphenoxy-poly (ethyleneoxy) ethanol from GAF Corporation

Trade name for ethyl cellulose from Hercules Powder.

After 2 to 3 minutes, the receiving sheet, which had a yellow positive reproduction of the original gray wedge, was deducted.

CH ₃

I SO ₂ -NC ₁₈ H _3n

Example 2

A photosensitive element was made which which had the following layers:

1. film base;

2. A layer like layer 2 in example 1, but instead of the yellow, bivalent, non-diffusing one Coupler of Example 1 the above divalent, non-diffusing magenta coupler was used;

3. In terms of type and composition, this layer was identical to layer 3 of Example 1;

0 9 δ Ί 0 / U 8 b 8

4. In terms of type and composition, this layer was identical to layer 4 of Example 1 / where this time however, the silver bromide iodide was sensitized to the green region of the spectrum.

The photosensitive element was exposed to green light through a continuously graduated gray wedge and in intimate connection with the receiving sheet with the developer solution of Example 1, as shown in Fig. 5, treated. After 2 to 3 minutes, the receiver sheet was peeled off, showing a positive magenta production of the original step wedge exhibited.

Example 3

9? 2 ^H 5 ■

^NC 18 ^H 3n

CH.

A photosensitive element was prepared which contained the had the following layers:

4O98'iO / U8b8

1. film base;

2. A layer like Layer 2 in Example 1, in which however, instead of the divalent, yellow, non-diffusing coupler of Example 1, the divalent, non-diffusing cyan couplers were used;

3. This layer was identical in terms of type and composition to layer No. 3 of Example 1;

4. This layer was in terms of type and composition identical to layer 4 of Example 1 with the exception that a silver bromide iodide was used which was used for the red Area of the spectrum was sensitized.

The photosensitive element was exposed to red light through a continuously graduated gray wedge and in intimate connection with the receiving sheet with the developer solution of Example 1, as shown in Fig. 5, treated. After 2 to 3 minutes, the receiving sheet was peeled off and it contained a positive cyan reproduction of the original gray wedge.

Example 4

A photosensitive element identical to the element of Example 1 was prepared With the exception of layer no. 3, which was applied in a layer thickness of 5.0 microns, while in Example 1 the the same layer had been applied at a very thin layer thickness of 0.5 microns. The light sensitive Element was exposed through a continuously graduated gray wedge and in intimate contact with the receiving sheet with the developer solution of ExampleΊ, which is a silver

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medium (sodium thiosulphate) in a concentration of 1.0 g / l as indicated in FIG. 5, treated. After 2 to 3 minutes, the receiving sheet was peeled off. It was found that developed on the receiving sheet and the Negative, although negative development had taken place, no positive dye image was formed and no transmission occurred.

Example 5

A photosensitive element was made which had the following layers:

1. film base;

2. A cyan-forming layer identical in type and composition to layer 2 of Example 3 was;

3. A sealing layer (barrier layer) which, in terms of type and composition, is identical to layer 3 of Example 3 was identical;

4. A red-sensitized photosensitive layer that was identical in type and composition to layer 4 of example 3;

5. A gelatin spacer layer 5 microns thick;

a

6. A / magenta dye-forming layer, regarding

Type and composition was identical to layer 2 of example 2;

7. A sealing layer (barrier layer) in terms of

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" ²⁵ " 23409U

Type and composition with layer 3 of the example 2 was identical;

8. A green-sensitized, photosensitive layer that was identical to layer 4 of example 2 in terms of type and composition.

The photosensitive element was exposed to a ray diagram with pure red and green spots. there has been a Developing solution prepared with respect to its composition was identical to that of Example 1 except that the concentration of sodium thiosulfate was increased to 2.0 g / l. The negative was in intimate connection with the receiving sheet of Example 1 treated with the developing solution as indicated in FIG. After 3 to 5 minutes, the receiving sheet was peeled off. In the areas exposed to red light was the pure Magenta dye has been transferred. The opposite was true in the. areas exposed to green light the pure cyan dye Have been transferred. No stain was contaminated by the dye associated with the other.

Example 6

The photosensitive element of Example 5 was made again, but with one change. The spacer layer 5 in Example 5 has been reduced in thickness from 5.0 to 3.0 microns. The exposure and the development were the same. After 3 to 5 minutes, the receiving sheet was peeled off. In the districts exposed to red light the magenta dye was transferred, but it was due to a co-transferred unwanted cyan dye discolored (mixed). In the districts that had been exposed to green light, the cyan dye was transferred,

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however, it was mixed with a cotransferred magenta dye.

Example 7

In this example, the photosensitive element des Example 5 with the 5.0 micron thick spacer layer between the two photoactive layers after exposure developed the same radiation pattern as in Example 5 in a developer solution, the concentration of silver solvent (Sodium thiosulfate) had been increased to 3.0 g / l. The results obtained showed that the same Color impurities as in Example 6 had been obtained.

Example 8
A photosensitive element was made as follows:

Layers 1 to 8 of the photosensitive element of Example 5, the following layers were applied:

9. A gelatin spacer layer 5.0 thick

Micron;
10. A layer producing the yellow dye which, in terms of type and composition, is identical to layer 2 of Example 1

was identical;
11. A sealing layer (barrier layer) which is identical to layer 3 of example 1 in terms of type and composition

was;
12. A non-sensitized photosensitive layer which is identical in nature and composition to layer 4 of the

Example 1 was identical;
13. A thin protective surface layer of gelatin.

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The light-sensitive layer was made with a ray diagram with a continuously graduated gray wedge and red, blue, green, blue-green, purple and yellow spots exposed. It was then combined with the receiver sheet of Example 1 and with the developer solution of the Example 5 as indicated in Fig. 5 is developed. After 3 to 5 minutes, the receiver sheet was peeled off, with one positive Reproduction of the original ray diagram for color and density values was obtained.

Examples 1, 2 and 3 above illustrate the three separate intranegative steps leading to the composite dye carry out the transfer according to example 8. Example 4 shows that the intranegative step between a silver source and a reactive layer spaced on the order of 3 microns at the indicated silver solvent concentration of sodium thiosulfate does not work. this shows that the individual elements function on the reaction-assisted silver transfer method. Example 5 shows that the solubility and distance parameters selected in Example 5 are undesirable intranegative Suppress transmissions. Example 6 shows that the solvent concentration parameter alone is not sufficient to — maintain — the preferred mode of transmission. That Example 7 shows that the distance parameter alone is not sufficient to maintain the preferred mode of transmission. obtain. Examples 5,6 and 7 show that the preferred intranegative transfer method is a function of a reciprocal Relationship between the distance and concentration parameters is. Example 8 then shows the overall process, as it happens according to the invention.

The transmission configuration represented by Figs. 1-4, serves only to explain a practical implementation

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form of the invention, to which the invention is not limited. It is readily apparent to the person skilled in the art that other transmission configurations can also be used, such as those specified, for example, in US Pat. Nos. 3,635,707 and 3,615,421, cf., for example, FIGS layer 10 is a gelatin or similar colloid matrix layer containing carbon black or other pigments in concentrations sufficient to provide sufficient density to protect the underlying photosensitive layers from further exposure to active light when removed from the camera ;

Layer 19 is a gelatin or similar colloid matrix layer containing TiO ₂ or other white opacifying agent in a concentration sufficient to form a white reflective layer covering layer 18;

Layer 20 represents an auxiliary layer which contains TiO ₂ in concentrations sufficient to prevent exposure of the underlying photosensitive layers to actinic radiation and which it contains in concentrations sufficient to mark the opacifier after development, which is dispensed in the developer composition from the container 21;

Layer 21 is a pressure breakable container, the one p-phenylenediamine color developer, an antioxidant, contains an alkali thickener, TiO and carbon black in such concentrations that a complete Development of the entire silver halide in the fully exposed areas is guaranteed, and if this is observed a uniform distance between the layers 13 and

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20 the underlying sensitive layers against others Actinic light exposure protects when removed from the camera;

The layer 22 is a transparent film carrier, for example made of a polyester, a polycarbonate, cellulose acetate and the like, with a thickness of 0.0635 to 0.2286 mm. (2.5 to 9 mils);

Layer 23 is a transparent film base similar to base 22;

Layer 24 is pressure sensitive Connection layer that makes the negative element permanent bound to the image-receiving sheet on the coversheet and to the developing tank.

Although the invention has been explained in more detail above with reference to certain preferred embodiments, however, it is clear to the person skilled in the art that these can be changed and modified in many ways without that this leaves the scope of the present invention.

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Claims (11)

Patent claims f \ jj Light-sensitive, unitary element which is transparent to actinic radiation and to an alkaline developing solution containing a color developer of the formula Y-CD wherein Y = H, -SO ₃ H or -COOH and CD is a p-phenylenediamine derivative radical, and contains low concentrations of a silver halide solvent, is sensitive, characterized by (a) a carrier; (b) a color-producing, nucleating colloid layer on the Carrier, the dispersed noble metal or noble metal sulfide particles and a non-diffusing, colorless, divalent (2-equivalent) coupler of the formula XCLB
contains where
, X = H, -SO-H, or -COOH C is a photographic coupler radical from the group of the 5-pyrazolone; the phenolic and open-chain ketomethylene coupler residues, which is substituted in the coupling position by the L radical, L is a sulfoxy, carboxy, oxy, azo, azoxy, thio or alkyl idenre st, and B denotes a photographically inert organic ballast residue of such a molecular size and configuration, which cause the coupler to be nondiffusible; (c) a cleaning colloid layer that is one with the oxidized Color developer contains reactive antioxidant; and 409810/0868 (d) a silver halide light recording layer for silver ion transfer which is non-diffusing Contains color former, which acts as a cleaner for the oxidized color developer during negative development with actinic Light irradiated areas, and for the transfer of a positive color image to a receiving sheet, whereby the formation reaction of the diffusible dye is initiated, supported by the reaction Transfer of silver ions by the silver halide solvent are released from the light-recording layer, onto the color-producing layer, which is partly due to the capacity of the nucleus-forming layer as a silver ion sinking point (receiving point) is supported, wherein the solvent pushes the silver ions and pulls the nucleating layer, whereby the Silver ion transport between the two last-mentioned layers is limited. 2. A photosensitive unitary element according to claim 1, characterized in that the color developer has the formula Y-CD wherein Y = -SO ₃ H, and the non-diffusing ₁ 2-valent, colorless coupler has the formula XCLB, wherein X = H and B denotes an aliphatic hydrocarbon radical having up to 30 carbon atoms, which makes the coupler lipophilic, and. that the coupler is dispersed in a high-boiling, photographically inert solvent. 3. A photosensitive unitary element according to claim 1 or 2, characterized in that it comprises a receiving sheet, which contains a mordant which immobilizes the dye released from the color-forming layer. 4. A photosensitive unitary element according to claim 3, characterized in that the receiving sheet is transparent so that 409810/0868 the product can be used as a monochrome test slide. 5. The unitary photosensitive member of claim 3 characterized characterized in that the receiving sheet is opaque. 6. Light-sensitive 3-color element that is opposite to a alkaline developer solution that contains a color developer and low concentrations of a silver halide solvent contains, characterized by: (a) a document; (b) 3-color arrangements on the base, which are cyan, Provide magenta and yellow dyes and are red-green and blue-sensitized, respectively; one (c) Colloid separating layer between the cyan, magenta and yellow dye providing assemblies; (d) each arrangement having a color-generating, nucleating layer- containing dispersed noble metal or noble metal sulfide particles, a non-diffusing colorless, divalent (2-equivalent) coupler of the formula XCLB, wherein X = H, -SO ₃ H or -COOH, C is a photographic coupler radical from the group of 5-pyrazolone, phenolic and open-chain ketomethylene coupler radicals, which is substituted in the coupling position by the L radical, L is a sulfoxy, carboxy, oxy, azo , Azoxy, thio or alkylidene radical, B means a photographically inert organic ballast radical of such a molecular size and configuration that the coupler is non-diffusible, the non-diffusing, colorless, divalent coupler being able to with one Color developer of the formula Y-CD to react, 40 9810/0868 wherein Y = H, -SO ₃ H or -COOH and CD is a p-phenylenediamine derivative radical; (e) a detergent colloid layer that is one with the oxidized Color developer contains reactive antioxidant; (f) a silver halide light recording layer for silver ion transfer, which contains a non-diffusing color former that acts as a cleaner for the oxidized color developer in the negative development of areas exposed to actinic light, and for the transfer of a positive one Color image on a receiving sheet, whereby the color formation reaction is initiated by supported by the reaction Transfer of silver ions by the silver halide solvent are released from the light-recording layer, onto the color-forming layer and partly through the capacity of the nucleating layer is supported as a silver ion sink point, the solvent being the Silver ions, pushes and pulls the nucleating layer, preventing the silver ion transfer between these two last mentioned layers is limited. 7. Photosensitive 3-color element according to claim 6, characterized characterized in that the non-diffusing, colorless, 2-valent Coupler has the formula X-C-L-B, where X = H and B is an aliphatic hydrocarbon radical having 5 to 30 carbon atoms means to thereby make the coupler lipophilic, the coupler being in a high boiling point, photographically inert solvent is dispersed, for the reaction with the color developer of the formula Y-CD, where Y = -COOH. 8. 3-color photosensitive element according to claim 6 for use with the color developer Y-CD, wherein Y = SO ₃ H. 409810/08 6 9. Photosensitive 3-color element according to one of the claims 6 to 8, characterized in that it is a receiving sheet which contains a mordant which immobile the dye released from the color-forming layers makes to form a positive 3-color dye image. · 10. Photosensitive 3-color element according to claim 9, characterized characterized in that the receiving sheet is transparent or opaque. 11. Color diffusion transfer process in a multicolor photosensitive element having at least 2 color sensitized silver halide emulsion layers, a non-diffusing, colorless, divalent coupler for each layer, and a nucleating layer adjacent to each of the silver halide layers for the formation of a positive colored dye image from the non -Diffusing colorless, divalent coupler associated with the silver halide layer for transport from the unexposed areas in the vicinity of the silver halide layers by oxidation of a p-phenylenediamine color developer in the presence of a silver halide solvent after exposure and negative development of the element, characterized that the transfer of silver ion in the reaction centers · ■ in another color-forming layer as that which is sensitive to the color of the document (the object), is avoided by reacting (a) Limit the concentration of the silver halide solvent to an amount which will support the silver ions into the closest adjacent color-generating layer, but not into the more distant color-generating layer Layer transported; 409810/0868 (b) 'the non-diffusing, colorless, bivalent Coupler arranged in the nucleating layer so that only the silver halide from the immediately adjacent Layer represents the reaction source; (c) the oxidized p-phenylenediamine, which is now nucleating on this Layer limited, is the only source represents for the positive dye color when coupling, whereby after coupling the remainder remains in the nucleating layer and the transport of the diffusible, allows positive dye image in the receiving layer; and (d) arranging the nucleating layer sufficiently close, around by pulling the silver ions one through the reaction to effect assisted silver ion transport, acting as a sink point for silver ions, while the more distant color-producing layer for the other silver halide emulsion is at a distance, which is beyond its capacity to act as an effective silver ion sink point. 409810/0868 Read 11 e