DE1190336B - Multilayer color photographic material containing dye developing agents for the color diffusion transfer process - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

G03c

German class: 57 b -18/11

Number: 1190 336

File number: E 27103IX a / 57 b

Filing date: May 26, 1964

Open date: April 1, 1965

The invention relates to a color photographic material specifically for dye developing agents color diffusion transfer methods employing. In the production of color images after the diffusion transfer method, it is known to use compounds which are im the same molecule both the chromophoric system of a dye and a residue with development properties contain. Such compounds are usually called "dye-developing agents" designated. Photographic materials containing such dye developing agents, generally consist of several photosensitive silver halide emulsion layers, one of which each is selectively sensitized to a particular region of the spectrum. Any emulsion layer is in effective contact with a dye developing agent. After exposure will be the photographic material treated with an alkaline solution and the latent image in the negative Image areas are developed with the dye developing agents, the latter in the negative Image areas are determined by the development, while they are imagewise in the unexposed areas diffuse to the surface and to form a positive color image on an image receiving or Image recording sheet are transferred. Such color diffusion transfer methods are e.g. Am U.S. Patents 2,559,643, 2,647,049, 2698,798, 2,774,668 and 2,983,606 been.

However, the dye residue of the dye developing agent used is not with regard to its color always completely pure in color. For example, purple dyes often absorb something in the blue and red part of the spectrum. The yellow and blue-green dyes do not only absorb blue or Red light. Such undesirable absorptions usually have the effect that the color images dark and unsaturated hues or hue defects, so that after different on known methods, e.g. mask methods,. Corrections need to be made. The invention was therefore based on the object of a photographic material which avoids the disadvantages mentioned To produce material that does not exhibit these defects. In particular, a material should be created that utilize the undesirable absorptions used in diffusion transfer photographic systems Dye developer is effectively corrected so that color images can be obtained which are clearer and more clear have deeper color tones than those with the popular

Multi-layer color photographic material
with dye developing agents for the
Color diffusion transfer process

Applicant:

Eastman Kodak Company,

Rochester, N. Y. (V. St. A.)

Representative:

Dr.-Ing. W. Wolff, H. Bartels

and Dipl.-Chem. Dr. J.Brandes, patent attorneys, Stuttgart 1, Lange Str. 51

Named as inventor:
Richard William Becker,
Rochester, NY (V. St. A.)

Claimed priority:
V. St. v. America June 27, 1963 (291 056)

known photographic materials containing dye developing agents.

It has surprisingly been found that the

The problem posed can be achieved if one of the light-sensitive silver halide emulsion layers of the color photographic multilayer material has a higher molar proportion of iodide in the form of mixed silver halide than in at least one of the other silver halide emulsion layers is used.

Therefore, according to the invention there is provided a color photographic material which is on a Layer support arranged one above the other red, green and blue light-sensitive silver halide emulsion layers as well as in effective contact with these dye developing agents contained in the molecule containing chromophoric groups and silver halide-developing groups and their color spectral sensitivity of the associated silver halide emulsion layers is substantially complementary, and which is characterized in that the silver halide in at least one of the Emulsion layers at least 1 mole percent more

509 537/348

3 4

Iodide in the form of mixed silver halide mainly consists of silver halide emulsion layers

holds as the silver halide in at least one of the silver bromide iodide and in which the blue em-

other of the silver halide emulsion layers. sensitive silver halide emulsion silver bromide iodide

As is known from the literature, can contain sawn, at least 1 mole percent iodide agreed more interimage effects are used to 5 comprising as the silver bromoiodide in the green and the color reproduction the subtractive color shifts red-sensitive emulsion layer. When driving here to improve. For example, Hanson has presented the photographic material of Invention and Horton in J. of the Opt. Soc. be of America, droppings usual ausentwickelnde Silberhalo- vol. 42, no. 9, uses p 663-669, September 1952 genidnegativemulsionen. The use of interimage effects used here before the term "mixed silver halide" refers to the correction of undesired absorptions from photographic to silver bromide iodide, silver chloride iodide, silver graphic dyes. It became bromochloride iodide or mixtures thereof. It has now been found that such desired intermediate mixed silver halide crystals mentioned here are particularly advantageous for image effects in the case of ver can also be referred to as "solid solutions" using the photographic material according to FIG. They exist, as can be generated by X-ray diffraction invention. search could be determined from homogeneous,

The molecular or atomic dispersions in the color photographic material of the invention

Dung used dye developing agents are crystalline compound in another in solid

known. At neutral pH values, they are in the hydro phase, in contrast to a heterogeneous mixture

Filamentous layers relatively non- diffusing, 20 of crystals of two crystalline compounds.

but diffuse in the presence of alkaline A "mixed" silver halide, e.g. B. silver bromide

Treatment solutions. The compounds function iodide and are therefore quite different from one

mere mixture of silver bromide and silver iodide in diffusion transfer photographic systems.

as a developing agent for exposed silver halide while now silver bromide iodide or other iodide

and as a dye. Mixed silver halides containing 25

Dye- developing agents which produce desired interimage effects in photographic effects are silver phisches material of the invention , iodide is not suitable as such.
can, are z. B. in the German Auslegeschrift For the production of the Süberhalogenidemul- 1168 768, in the Australian patent specification 220 279, sion layers and other layers of the fiction of the German patent specification 1 036 640, the British 30 according to photographic material, including patents 804 971 and 804 973 to 804,975 of the layers containing the dye developer substances as well as the French patent specification 1168 292, intermediate layers, top layers and the like . These dye-developing substances can contain a wide variety of hydrophilic, organic stamps, all of which contain a chromophoric system. Colloids can be used as binders. Before or a (molecular) dye residue and at least 35 gelatin as a hydrophilic colloid is at least a residue with developer properties. Uses. Other suitable colloids exist, for. B. from particularly suitable dye developing agents are polyvinyl alcohol or its water-soluble Deri- those whose dyestuff radicals from an azo or vaten and copolymers, water-soluble poly-anthraquinone dyestuffs and their silver halides, such as. B. polyacrylamide, imidized polygenide -developing residue from a hydroquinone residue 40 acrylamide, etc., and other water-soluble film, forming substances, the water-permeable layers

The form for the production of photosensitive, such as. B. colloidal albumin, water-soluble

Emulsion layers of at least one of the silver borrowed cellulose derivatives, etc. Can also

halide emulsion layers of the mixtures according to the invention of two or more of the colloids

silver halide 45 used in photographic material. Dye developers can move into

contains at least 1 mole percent more iodide in the light-sensitive silver halide emulsion

In the form of mixed silver halide crystals and layers or in separate layers,

expediently predominantly (ie at least 50 mol- those adjoining the silver halide emulsion layers

percent) mixed silver halide boundaries containing iodide.

Genide crystals, in which the iodide is about 1 to 20 mol. 50 Suitable image-receiving layers consist e.g. B. percent of mixed silver halide crystals form from linear polyamides, proteins such. B. gel and at least about 1 mol percent more thereof in tine, polyvinylpyrrolidones, poly-4-vinylpyridine, the layer in question is present than in mixed polyvinyl acetate, polyvinyl alcohol, cellulose acetate, th silver halide crystals in at least one polyvinyl salicylal, partially hydrolyzed polyvinyl of the other silver halide emulsion layers. In acetate, methyl acetate, methyl cellulose, and the rest of the regenerated form, smaller or subordinate men cellulose, carboxymethyl cellulose and oxethyl cellulose, based on mole percent, of silver chloride, loose or mixtures of these substances. These imaging silver bromide, silver iodide, or mixtures thereof, can be coated on a separate support of the type also described in such higher (molar) iodide proportions above for the mixed silver halide emulsions 60 invention containing photosensitive materials. It used to be. The emulsion layers, the transparent as well as the opaque supports, mixed materials containing small amounts of iodide can be used. Receivers also contain silver halides , can also leaves, which release an acidic compound in a certain mixed halide as well as silver chloride, silver rate, as in the USA. Bromide , silver iodide or mixtures thereof according to 65 Patent Specification 2,584 030 described, specially kept. Photo- have proven to be particularly advantageous. Such acidic materials are generally found to be graphic materials in which the silver halide in layers on the receiving sheet below is in all of the light-sensitive ones that receive the dye-developing agent

Layer arranged, being expediently between the acidic layer and the one containing a pickling agent Layer an intermediate layer is provided to control the release of acidic compounds. The acidic compounds serve to remove residual amounts of the alkaline activator on the receiving sheet to neutralize.

Otherwise, the multi-layered color material, sensitized for the various partial colors, is structured in such a way that as is known for the color diffusion transfer process.

In Fig. 1 shows the structure of a photographic material according to the invention. In Fig. 1 is also an image-receiving sheet, upon which the dye images from the surface of the photosensitive Material are transferred, as well as a sleeve-shaped container shown, which is used for activation required material and that between the light-sensitive material and the image-receiving sheet introduced or placed between the two.

In the one shown in FIG. 1 material shown is applied to a carrier 10, a layer 11, the one Contains cyan dye developing agent. A layer 12 is arranged above the layer 11, which contains a red sensitive silver halide emulsion layer. There is one above layer 12 Intermediate layer 13 and over layer 13 a layer 14 which is a magenta color developing agent contains. On the layer 14 there is a layer 15 which consists of a green-sensitive silver halide emulsion layer consists. An intermediate layer 16 is applied over layer 15 and a layer 17, which contains a yellow dye developer, is applied over layer 16 contains. Above the layer 17 is a layer 18, which consists of a blue-sensitive Silver halide emulsion layer. Finally, a protective layer 19 is applied over the layer 18. The recording sheet consists of a carrier 23 on which a pickling agent is contained Layer 22 is located, which is the dye images from the photosensitive material during development takes up when photosensitive material and receiving sheet are stacked on top of each other. There is a breakable sleeve between the photosensitive material and the receiving sheet 21, which have an activator 20, e.g. B. contains a viscous, alkaline aqueous mixture.

After the image-wise exposure of the photosensitive material has taken place, the destructible sleeve can be emptied by passing the arrangement shown in the drawing between rollers, which are provided in the camera itself or outside the same, with the activator solution uniformly distributed over a certain area of the photosensitive material while the The recording sheet and the photosensitive material are on top of each other. The activator solution permeates layers 11 to 19, whereupon the latent Develop images into silver images and the dye developers in the adjacent layers 11, 14 and 17 are set or not in the areas corresponding to the latent image or the negative areas, respectively made diffusing and the dye developer in the remaining or positive image areas imagewise and transferred in register to the receiving layer 22 of the receiving sheet.

The photographic material can contain colorless auxiliary developing agents contained in the emulsion layers, coating layers or intermediate layers. Such auxiliary developing agents are known. to they include B. Compounds such as phenylhydroquinone, 2-oxyphenylhydroquinone, phenoxyhydroquinone, 4-methylphenyl hydroquinone, dodecyl hydroquinone and the like.

The photographic material according to the invention is advantageously used in the presence of Onium compounds developed, these generally being added to the alkaline activator mixture or incorporated into the image-receiving sheet. Suitable onium compounds are known. They include quaternary phosphonium, tertiary sulfonium, and quaternary ammonium compounds. The image-receiving sheet used to receive the dye-developer transfer images can development inhibitors, such as e.g. B. Mercaptoazole or equivalent Compounds included.

The F i g. 2 through 5 of the drawing show density-log E curves of that shown in Fig. 1 in the processing of photographic materials Type of dye images transferred to image receiving sheets. To get these curves a photographic material of the type shown in FIG. 1 described structure separated with red, green, blue and white light in an intensity dial sensitometer and, as in the following example described, developed with an alkaline solution, whereupon the dye developer images obtained on an image receiving sheet can be transferred. The density log E curves the dye images on the image-receiving sheets were determined in detail according to that of Hanson and Horton in J. of Opt. Soc. of America (supra).

Figures 2 and 4 show typical density log E curves of cyan and purple dyes transferred to image receiving sheets, the with negative photographic materials in which the individual silver halide emulsion layers no significant difference in mole percent iodide of the mixed Contained silver halides. Figures 3 and 5 of the drawings show characteristic density log E curves of cyan and magenta dyes that of photographic Materials were transferred to image receiving sheets and the interimage effects that can be achieved with this material. The in the F i g. 3 and 5 shown interframe effects are expressed in clear or brighter red or green tones in the transmission images. In the F i g. 2 and 3 means the The solid curve is the blue-green curve of the neutral scale read through a red filter, while the dashed curves in FIG. 2 and 3 each show the blue-green curve of the read through a red filter Red scale mean. The solid curves of FIG. 4 and 5 represent the purple curves of the the neutral scale read by a green filter, while the dashed curves in FIG and Fig. 5 represents the purple curves of the green scale obtained by reading the green scale through a Green filters were obtained.

The improvements obtained by using the photographic material of the present invention are not alone in the green and red over-

colors, but also affect the blue colors. The position of the photosensitive silver halide emulsion which contains the highest mole percent iodide of the mixed silver halide in the present three color system can be varied widely. Although the blue-sensitive silver halide emulsion preferably contains the highest mole percent iodide, the green-sensitive or red-sensitive silver halide emulsion layer may also contain the highest iodide content. Is it z. For example, if you want to achieve interimage effects that are monitored by the blue and / or red-sensitive emulsion, the emulsion with the highest iodide content will be placed in the green-sensitive layer . Correspondingly, in order to achieve advantageous interimage effects which are monitored by the green- and / or blue-sensitive emulsion, the emulsion with the highest iodide content can be accommodated in the green-sensitive layer. Correspondingly, in order to achieve advantageous interimage effects which are monitored by the green- and / or blue-sensitive emulsion , the emulsion with the highest iodide content can be accommodated in the red- sensitive emulsion layer. It is only necessary that one of the silver halide emulsions of the photographic material contain at least one mole percent more iodide in the form of mixed silver halide crystals than at least one of the other silver halide emulsion layers. The following example is intended to explain the invention in more detail.

example

There have been several photographic color films prepared in the Fig. 1 (layers 10 to 19) shown construction, by providing a backing layer provided with a cellulose acetate film was coated in succession with the individual layers.

1st Cyan dye developer layer
(corresponding to layer 11 of FIG. 1)

4. Magenta dye developer layer
(corresponding to layer 14 of Fig. 1)

4 - propoxy - 2 - [p ( β-oxyquinonylethyl) - phenylazo] 1-naphthol was used as the magenta dye developing agent. The dye developing agent was in a high boiling solvent, such as. B. Nn-butyl acetanilide, dissolved and dispersed in gelatin. The dispersion was applied to the intermediate layer in such a way that about 0.09 m ^{2 of} the layer accounted for 77 mg of the dye developer substance and 77 mg of gelatin.

5. Green sensitive emulsion layer
(corresponding to layer 15 of Fig. 1)

A developing gelatin-silver bromideiodide negative emulsion sensitized to green light was applied to the magenta dye developer layer such that 108 mg of silver and 80 mg of gelatin accounted for ^{about 0.09 m 2 of the layer.}

a ₅ 6th intermediate layer

(corresponding to layer 16 of Fig. 1)

This layer consisted of a gelatin layer containing 150 mg of gelatin per approximately 0.09 m ^{2 of support area} .

7. Yellow dye developer layer
(corresponding to layer 17 of FIG. 1)

1-Phenyl-3-Nn-hexylcarboxamido-4- [p- (2 ', 5'-dioxyphenethyl) phenylazo] -5-oxypyrazole was used as the yellow dye developer. The compound was dissolved in a high boiling solvent such as. B. Nn-butyl acetanilide, dissolved and dispersed in gelatin. The dispersion was applied to the intermediate layer in such a way that about 0.09 m ^{2 of} the layer accounted for 50 mg of the dye developing agent and 50 mg of gelatin.

As a cyan dye developer was 5,8-dioxy-1,4 - bis - [(ß - hydroquinonyl - <* - methyl) -äthylamino] - used anthraquinone. The dye developing agent was dissolved in a high boiling solvent, e.g. B. Nn-butyl acetanilide, dissolved and dispersed in gelatin. The dispersion obtained was applied to the carrier in such a way that 128 mg of dye developer substance and 141 mg of gelatin were ^{applied to approximately 0.09 m 2 of carrier area.}

2. Red sensitive emulsion layer
(corresponding to layer 12 of Fig. 1)

A developing gelatin-silver bromideiodide negative emulsion which had been sensitized to red light was applied to the cyan dye developer layer in such a way that 210 mg of silver and 155 mg of gelatin accounted for about 0.09 m * support area.

3rd intermediate layer (corresponding to layer 13 of FIG. 1)

This layer consisted of a gelatin layer with 200 mg of gelatin on an approximately 0.09 m ^{2 support} surface.

8. Blue sensitive emulsion layer
(corresponding to layer 18 of FIG. 1)

A developing gelatin silver bromide iodide negative emulsion which was intrinsically sensitive to blue light was applied to the yellow dye developer layer in such a way that 55 mg of silver and 41 mg of gelatin accounted for ^{about 0.09 m 2 of the layer.}

9. Protective layer
(corresponding to layer 19 of FIG. 1)

The layer consisted of the colorless auxiliary developing agent 4'-methylphenylhydroquinone dispersed in gelatin and contained 20 mg of the developer ^{compound and 40 mg of gelatin over about 0.09 m 2 of the layer.}

To show the improved interimage effects obtained by using higher mole percent Iodide in the mixed silver halide emulsion layers of the photographic of the present invention Material were found in the blue

sensitive emulsion layer, corresponding to layer 18 from Fig. 1, various amounts of iodide in silver bromide iodide used, while the silver bromide iodide the red-sensitive and the green-sensitive Layer (layers 12 and 15 of Figure 1) contained 4.5 mole percent iodide. The different Color films were separated in an intensity dial sensitometer with red, green, blue and exposed to white light, whereupon the exposed films are treated by treating the surfaces with an alkaline Activator solution was developed, while simultaneously over the surface of the to be developed Films image receiving sheets were arranged, which were made of a white pigmented cellulose acetate support which had a gelatin layer containing a mixture of poly (4-vinylpyridine) as a mordant and l-phenyl-5-mercaptotetrazole as a development inhibitor contained. The one between the image receiving sheets and the exposed negative films alkaline activator was left to act for 2 minutes at about 21 ° C, whereupon the image reception sheets and the developed films were separated from each other again. The alkaline activator consisted of an aqueous solution containing 3.5% highly viscous oxyethyl cellulose, 4.5% sodium hydroxide, 2% benzotriazole, 2% 1-benzyl-2-picolinium bromide and contained 1% sodium thiosulfate. The reflection densities of the graduated scales of the Transferred dye developer images on the receiving sheets were then measured and the measured values in analytical densities for the particular ones contained in the corresponding color images Cyan, magenta and yellow dyes converted; the analytical densities eventually became plotted against logarithmic exposure to the usual sensitometric reversal curves obtain. In order to determine the interimage effects, the curves for each of the color bars were compared with the Neutral curve compared. Specifically, the cyan dye was on the neutral scale with the cyan dye in the red scale and the purple-red dye in the green scale. It was found, that the coatings containing the higher mole percent differed significantly in density at the same exposure (namely 0.8) when comparing the cyan dye in the neutral scale and curves representing the cyan dye in the red scale and when comparing the Curves showing magenta dye in the neutral scale and the magenta dye in the green scale showed. Such differences in density with the same exposure represent interimage effects. They are reproduced in the drawing by FIGS. 2 to 5. The F i g. 2 and 4 relate to a photographic one Material whose mixed silver halide of the blue-sensitive emulsion is not higher Has iodide content. 3 and 5, on the other hand, relate to a photographic material, its blue-sensitive emulsion layer has a higher iodide content. Doing so will be essential greater interimage effects achieved, which are expressed in that the red and green hues turn out to be considerably clearer and brighter in the color transfer images.

The following table shows the improved cyan and magenta interimage effects as a function the iodide content in the mixed silver halide of the blue light-sensitive emulsion.

Mole percent iodide

in the

blue sensitive
Emulsion layer *

4.5

+0.03
+0.14
+ 0.20

M _n -

-0.07

0
+ 10

* The red and green insensitive emulsions contained 4.5 mole percent iodide in all test films.

** C _n = 0.8 density of the blue-green curve of the neutral scale. C _T = density of the blue-green curve of the red scale at

log exposure value where C _n - 0.8.
*** M _n = 0.8 density of the purple curve of the neutral scale. M _g = density of the magenta curve of the green scale at the log exposure value where M _n = 0.8.

The interimage effects obtainable with the photographic material of the invention are as desirably known because they produce improved color unity in subtractive color processes. With the According to the invention photographic material it is possible to produce such intermediate image effects in the simplest possible way and most efficient way to produce.

Claims (6)

Patent claims: 1. Color photographic material arranged one above the other on a support red, green and blue light-sensitive silver halide emulsion layers as well as in contact with this dye developer has the chromophoric groups and in the molecule Contain silver halide developing groups and their color of the spectral sensitivity of the associated silver halide emulsion layers is substantially complementary, thereby characterized in that the silver halide of at least one of the emulsion layers contains one mole percent more mixed silver halide iodide than the silver halide at least one of the other silver halide emulsion layers. 2. Material according to claim 1, characterized in that the more iodide containing Emulsion layer contains about 1 to 20 mole percent iodide. 3. Material according to claims 1 and 2, characterized in that the dye developer substance each incorporated in a layer adjacent to the associated emulsion layer is that the dye developing agents contained in the layer have a molecular hydroquinone residue contain, and that the silver halide of the blue light-sensitive emulsion layer more Each of the red and green sensitive emulsion layers contains iodide as the silver halide. 4. Material according to claim 3, characterized in that the silver halide of the emulsion layers consists predominantly of silver bromide iodide. 5. Material according to Claims 1 to 4, characterized in that the dye developer substance in the gelatin layer adjacent to the red light-sensitive emulsion layer made of 5,8-dioxy -1,4 - bis - [(^ -hydroquinone -1- «-methyl) -äthylamino] -anthraquinone, the dye developing 509 537/348 substance in the gelatin layer adjacent to the green light-sensitive emulsion layer of 4 - propoxy - 2 - [p - (ß - oxyquinonyl-ethyl) -phenylazo] -l-naphthol and the dye developer substance in the gelatin layer adjacent to the blue light sensitive emulsion layer of Nn- Hexylcarboxamido - [4 - ρ - (2 ', 5'-dioxyphenethyl) phenylazo] -5-oxypyrazole consists. 6. A method for processing the material according to claims 1 to 5, characterized in that that the development is carried out in the presence of an onium compound. 1 sheet of drawings 509 537/348 3.65 © Bundesdruckerei Berlin