DE2307738B2 - PHOTOGRAPHIC RECORDING MATERIAL FOR COLOR DIFFUSION TRANSFER PROCESS - Google Patents

Description

/ | pCH ₂ CONH-I J

OCH ₃

OH

(\ -CH, CONH

OH

OH

(CH ₂ J ₄ -CONH

NN-QH ₅

CONH

Cl-

(CH ₂ UCNH

OC ₅ H ₁₁

OH

Cl

CHXONH -Τ VNH

NHCOC ₃ F ₇

OH

16. Recording material according to claim 7, characterized in that the onium compound, in particular quaternary ammonium compound, is contained in the image receiving layer.

17. Recording material according to claim 16, characterized in that it is used as an onium compound contains an immobile polymer with onium groups.

18. Recording material according to claims 16 and 17, characterized in that the image receiving layer contains ^{25 to 1000 mg of onium compound / 0.0929 m 2 of support surface.}

The invention relates to a photographic recording material for color diffusion transfer processes, consisting of a support, at least one light-sensitive silver halide emulsion layer, at least one diffusible, colorless or weakly colored, image dye-providing Silver halide developing agent, the light absorption of which is variable after exposure, in the Silver halide emulsion layer or a layer adjacent thereto and, if appropriate, further ones Layers. The invention further relates to a photographic recording unit for color diffusion transfer processes, consisting of

a) a light-sensitive recording part,

b) an image receiving layer and

c) at least one splittable by the action of pressure Container with alkaline developing agent

liquid for the recording material.

It is well known, e.g. B. from US-PS 29 83 606 and 32 25 001, for performing color diffusion transfer processes to use color photographic recording materials containing dye developer compounds, d. H. Compounds with a dye and a developer residue contain. Disadvantages of these dye developer compounds is that they are colored due to the dye residue and therefore absorb light, which is why they are not in the or the silver halide emulsion layers of the recording material can be accommodated, but only in special layers under the silver halide emulsion layer (s), so none Absorption competition between the dye-developing compounds and the superhalide photosensitive emulsion layers in contact therewith he follows.

It is also known, for example from U.S. Patents 3,30,7,947 and 3,579,334, for performing dye diffusion transfer processes Color developer compounds to be used by a content of Acyl groups are characterized. The acyl groups are hydrolyzed under strongly alkaline conditions, and the color of the color developer thus changes to the image-forming color. Such a one Hydrolysis or cleavage of an acyl group from color developing agents raises numerous Problems. The main disadvantage is that if the hydrolysis does not proceed to completion, the dye image transferred to the image-receiving sheet with the dye of a second hue is contaminated, namely the hue of the original color developing agent.

Also known are colorless or leuco color curlers, z. B. from US-PS 29 92 105, which, however, an oxidizing agent present in the photographic system require in order to convert the leuco dye into the ultimately present image dye. The disadvantage here is that these known leuco color developer compounds lead to premature oxidation tend to dye, which is due to ambient or atmospheric oxygen. One such oxidation of the leuco dye results in the formation of a dye that has sensitivity of the photographic material is lowered due to its light filtering effect when it occurs in a silver halide emulsion layer. Another disadvantage is that it is not insignificant raises technical problems, color developer compounds of the known type with the desired Produce shade for all three color-forming layers.

The object of the invention is for color diffusion transfer processes indicate certain photographic recording materials, their image dye-providing Silver halide developer compounds are colorless or only slightly colored and a simple, enable rapid and complete change in light absorption after exposure, without the need for a hydrolysis or oxidation reaction.

The invention is based on the knowledge that the specified object can be achieved in that Color developing agents are used whose dye residues consist of indophenol dye residues, because the indophenol on the image-receiving sheet can easily be reacted with an onium compound forming an image dye consisting of an onium indophenoxide, so that in its spectral Absorption-modifiable color developers are available that work in the desired image dye are far easier and more effectively transferable than the known color developers which require hydrolysis comparable type, and furthermore, in contrast to the known leuco color developers. do not require oxidizing agents and are therefore not prematurely converted into the desired image dye can be.

The invention relates to a photographic recording material for color diffusion transfer processes, consisting of a support, at least one light-sensitive silver halide emulsion layer, at least one diffusible, colorless or weakly colored, image dye-providing Silver halide developing agent, the light absorption of which can be changed after exposure, in the silver halide emulsion layer or a layer adjacent thereto and, if appropriate, others Layer, which is characterized in that the developing agent is a compound of the following Formula is:

D - (insulating link) - (SlD)

in which D means an aromatic radical with a silver halide developer function, SlD an indophenol dye radical, and in which the isolating link is one which interrupts the resonance system of the connection Atom grouping is.

In the developer compounds used for the production of a photographic recording material according to the invention, the indophenol dye residue is thus connected to the residue D via an insulating link. The insulating connecting link, which may also be referred to as achromophores member does not constitute a color-forming bond, but any system interrupts a conjugation or resonance that a residue of hydroquinone, extending from the Azomethinrest of lnsophenolfarbstoffrestes the developer remainder,? .. example. As a result, any influence of the developer residue on the color characteristics of the azomethine group of the indophynol dye residue is practically eliminated. The insulating link, which preferably forms part of the indophenol dye residue, can consist of any link which interrupts the resonance system, for example a link of the type known from US Pat. No. 3,255,001.

The presence of an azomethine group is characteristic of the indophenol dye residues Formula - C = N -. This means that among indophenol residues Dye residues are to be understood. which z. B. from an indophenol of the following Derive formula:

(Kupp) = N -Ar-OH

in which Ar is an arylene radical having 6 to 20 carbon atoms and Kupp, a color coupler moiety that is bonded to the nitrogen atom in its coupling position is.

The hydroxyl group is preferably in the p-position to the nitrogen atom.

Those which can be used for the production of photographic recording materials according to the invention Developer compounds of the specified structure are distinguished by the fact that they are colorless or have at most only little color absorption and after exposure of the recording material, in which they are housed, by bringing them into contact with a positively charged compound, preferably with an onium compound, can be converted into image dyes, which are excellent Image characteristics including excellent stability and density.

According to a particularly advantageous embodiment of the invention, the recording material contains at least one developer compound of the following formula:

D - (insulating link) - (K upp) = N - Ar - OH

the individual parts of which follow the terms already given; to have.

Advantageously, a record? material according to the invention on:

a) a blue sensitive silver halide emulsion layer and one providing a yellow dye InHophenol color developing agent,

b) a green-sensitive silver halide emulsion layer and one a magenta dye supplying indophenol color developing agent as well as

c) a red sensitive silver halide emulsion layer and one providing a cyan dye Indophenol color developing agent,

with the proviso that the indophenol color developing agents in the emulsion layers or in these adjacent layers may be included.

Such recording materials can advantageously be part of photographic recording units Door color diffusion transfer process, which is why the subject of the invention further is a photographic recording unit door color diffusion transfer method, which consists of

a) a light-sensitive recording unit,

b) an image receiving layer and

c) at least one container with alkaline developing liquid which can be split open by the action of pressure Door the recording material,

which is characterized in that the photosensitive Recording part consists of one of the recording materials described.

The production of color photographic images using a recording material or a Recording unit according to the invention is carried out in such a way that the recording material or the recording unit

a) exposed to the correct image,

b) with an alkaline developing solution to develop the silver halide emulsion layer or layers - treated,

c) at least some of the diffusible color developer compounds present in imagewise distribution diffuses into the image receiving layer and

d) the color developer compounds after the imagewise exposure of the recording material or bringing the recording unit into contact with an onium compound.

The onium compounds can advantageously be accommodated in the image receiving layer and from a mordant for the Indophenoi dye developer compounds exist.

When using a recording material or a recording unit according to the invention are pholographic images with onium indophenoxide dyes obtained, which can be represented by the following structural formula:

D - (insulating link) - (SID) ^α Μ

where D, the insulating link and the remainder SID have the meaning given and M is an onium group is.

The onium indophenoxide dyes preferably have the following formula:

65 D- (insulating link) - (Kupp) = N-Ar-O M

where D, the isolierei.de link, the rest SID, (Kupp), Ar and M have the meanings already given.

M can be a sulfonium, phosphonium or, preferably, a quaternary ammonium radical.

After the onium indophenoxide in the image receiving layer have been generated or have been transferred to the image receiving layer the developer residues D are in the oxidized or unoxidized state.

Preference is given to producing the onium indophenoxide dyes quaternary ammonium salts, quaternary phosphonium salts or tertiary sulfonium salts used as onium salts, in concentrations which are necessary for all indophenol compounds in the recording material to convert into onium indophenoxide.

If onium compounds containing immobile or ballast groups are used in an image receiving layer, they are preferably used in concentrations of about 25 to about 1000 mg per 0.0929 m ^{2 of} substrate surface, in particular in concentrations of about 50 to about 500 mg per 0.0929 m ² Layer support surface used, of course, the ratio of onium atoms to the molecular weight of the compound used must be taken into account.

If the onium compounds or onium salts are in the form of solutions, e.g. B. in the work or When developing solution is applied, it has been found to be useful to add the compounds to be used in concentrations of about 0.01 to about 5 percent by weight for complete to achieve conversion of the indophenols into onium indophenoxides, the most favorable in the individual case Concentration of onium compound of course in turn depends on the concentration of the or the Dyes in the recording material and the ratio of onium residues to the molecular weight of the Onium compound depends.

Advantageously, color photographic recording units according to the invention can except at least one of the indophenol dye developer compounds to be used according to the invention at least contain a silver halide auxiliary developing agent composed of a reducing agent.

The drawing serves to explain the invention in more detail. In detail are shown in:

F i g. 1 typical absorption shifts associated with a yellow indophenol dye yielding Dye developer compound with an open-chain ketomethylene coupler residue (line Y). one one purple indophenol dye-forming dye-developing compound having a pyrazolone color coupler moiety (Line M) and a cyan indophenol dye-forming dye developing compound with a phenolic color coupler residue (line C) can be achieved, with the absorption characteristics of the indophenol dye developing agent in the recording material are represented by the lines SY, SM and SC, and the Absorption characteristics after contact with an onium compound represented by the lines Y, M and C. (for the purpose of further details of the absorption shifts, reference is made to DT-OS 22 38 051),

F i g. 2 and 3 show typical absorption characteristics of dye developing agents of the following Examples 2 (compound I) and 8 (compound IV),

509 584/373

23

ίο

F i g. 4 to 6 a particularly advantageous photographic recording unit according to the invention.

In that for the dye developer compounds used in the present invention given formula

D - (insulating link) - (SID)

the aromatic radical with a silver halide developer function indicated by D can be hydrolyzed Have residues. Preferably, D consists of a disubstituted aromatic radical, in particular a naphthalene or preferably a phenylene radical which is disubstituted, the substituents from hydroxy radicals, primary amino radicals or alkylamino radicals, including substituted alkylamino radicals and where the second Substituent is preferably in the ortho or para position.

In the one specified for the indophenol dye residue

^Formula (Kupp) = N-Ar-OH

the arylene radical represented by Ar can optionally also be composed of a condensed aromatic Remainder exist or can be substituted by condensed aromatic residues, where it also applies that Ar is preferably an optionally substituted phenylene radical, which is advantageously replaced by a or more halogen atoms can be substituted or by radicals which contain halogen atoms, and although preferably in the ortho or meta position of the ring.

The color coupler residue (Kupp), which has a link to the aromatic residue with a silver halide developer function is bonded can be a conventional phenolic color coupler radical or a pyrazolone color coupler radical or a pyrazolotriazole color coupler radical or a conventional open-chain methylene color coupler radical, wherein the color coupler group is bonded to the nitrogen atom through a carbon atom in the coupling position of the color coupler group.

Those used for the production of color photographic recording materials according to the invention Diffusing dye developing agents will diffuse upon exposure to an alkaline developing solution into an image-receiving layer, if not the developer residue by reaction with developable material Silver halide or a redox compound is oxidized.

The coupling positions of the color coupler remnants are known to be the positions in the color coupler remainder, capable of reacting or coupling with oxidized dye developing agent. The coupler remains can typically consist of phenolic dye coupler residues, including naphtholic Color coupler residues that couple in the 4-position or consist of open-chain ketomethylene color coupler residues, which are able to couple to the carbon atom forming the methylene radical, e.g. B. the with a “+” carbon atom of the radical indicated below

Il

—C — CH,

or from 5-pyrazolone color coupler residues, which also couple at the carbon atom in the 4-position.

Typical color coupler compounds made with p-aminophenols capable of reacting to produce an indophenol dye residue are, for example

from the following US-PS 2407 210, 22 98 443,

28 75 057, 32 65 506, 34 08 194, 34 47 928, 23 69 489,

26 00 788, 29 08 573, 30 62 653, 34 19 391, 35 19 429,

3152 896, 24 23 730, 24 74 293, 34 76 563, 27 72 162, 30 02 836 known.

In the given formula

(Kupp) = N - Ar - OH

As already stated, ίο is preferably the remainder a common aromatic dye developing agent, particularly an aminophenol dye developing agent or a phenylenediamine dye developing agent, with the proviso that the aromatic radicals of these dye developing agents can be substituted in a conventional manner. According to a particularly advantageous embodiment According to the invention, Ar is the residue of a conventional aminophenol developing agent, the aromanic Rest can be substituted in an advantageous manner in the ortho and / or meta position, in particular by halogen atoms and / or radicals containing halogen atoms. Such developer compounds are described in more detail in DT-OS 22 38 051, for example.

Typical yellow dye-forming indophenol dye-developing compounds which z. B. excellent for the production of recording materials with three differently sensitized emulsions sion layers can be represented by the following structural formula:

D- (insulating link) - (KMK) = N-Ar-OH

where D, Ar and the insulating link have the meaning already given and (KMK) is an open-chain Ketomethylene color coupler radical, which is connected to the nitrogen atom of the via its coupling position given formula is bound. A typical dye developing agent of this type is, for example the compound I given below:

Compound I

OH

OCH ₃ COCCONH ^ O)

-CH ₅ CONH-K O

N /

OH

Br-

OH

Typical magenta dye-forming indophenol dye developer compounds that advantageously for the production of recording materials with three different sensitized Emulsion layers are suitable and advantageously with a green-sensitive silver halide emulsion layer can be in contact, for example, dye developer compounds of the following formula:

D- (isolating link) - (PYZ) = N-Ar-OH

where D, Ar and the isolating link have the meaning already given and (PYZ) is a pyrazo

23 07 73ö

is ion or pyrazolotriazole color coupler radical, preferably a color coupler radical with one of the two the following remains:

or

Br-

OH

Compound V

- (CH ₂ U-CONH-ZN

NN-QH ₅

CONH

Vl

Typical dye developing agents of this type are the following compounds IU and IV:

Connection IH O

OH

wherein the 4-position in each case to the nitrogen atom of Dye developer formula is bound. Typical dye developing agents of this type are the developer compounds II and V.

Connection 11

_O | -CH ₂ CONH- / N-NH

CH ₂ CONH

NHCOC ₃ F ₇

and

Compound IV O

NHC ^ f VoC ₅ H ₁₁

Cl

35 OH

Typical cyan dye-forming indophenol dye developer compounds that Excellent for the production of recording materials with three differently sensitized emulsion layers and with the red-sensitive one Silver halide emulsion layer of such a recording material are in contact can be represented by the following structural formula:

D- (insulating link) - (PhK) = N-Ar-OH

where D, Ar and the insulating link have already given meaning and (PhK) is a phenolic Color coupler remainder is. that via its coupling position to the nitrogen atom of the formula given is bound.

The indophenol dye developing agent used in the present invention can be produced by various processes.

One method is to use a masked silver halide developer compound to condense with a color coupler, the condensation product with an aminophenol, in particular p-aminophenol, implement and then remove the masking residues of the silver halide developer residue.

It is also possible to first react the aminophenol with the color coupler and then react the reaction product with the masked silver halide developing agent to condense. The color coupler can be reacted with an oxidized aminophenol to form a dye, or if color couplers with active methylene groups are used, their active methylene groups have been halogenated, the color couplers can also be reacted with unoxidized aminophenols will. Such methods are described in more detail in DT-OS 22 60 202 and 22 60 204.

For the production of photographic recording materials and recording units according to dei Invention suitable indophenol dye developer compounds can finally also after Process described in DT-OS 22 60 203 can be produced. After that, the first söge called oxichromogenic developer compounds, which are then chromogenic with the production of voi Indophenol dye developing agents can be oxidized, for example by air oxidation or an electrochemical oxidation.

2

The preparation of dye developer compounds (by reacting a masked developer compound with a dye component by condensation is, for example, from the »Journal of Chemical and Engineering Data ", Vol. 9, No. 2, 1964, pp. 232-238. After the condensation may be the masking residues that perform the superhalide evolution function masking residues can be easily removed, as dyes, such as they have been used so far, e.g. B. azo dyes and anthraquinone dyes relatively stable under the conditions which are necessary for the removal of the masking residues.

It has now been found that dye developer compounds with indophenol dye residues also by condensation reactions starting from masked developer compounds can, if mild hydrolysis conditions are observed, in which the pH value between about 7 and about 10 is held, and if the masking residues are those residues which under these conditions hydrolyze easily, e.g. B. masking residues associated with the silver halide developer residues Form carbonate, oxalate or trifluoroacetate salts. In contrast, masking residues, such as. B. Acetoxy radicals are used to mask the silver halide developer radicals, so is hydrolysis of the masking residues are generally associated with a considerable degradation of the indophenol.

The hydrolysis is preferably carried out with a mild hydrolysing agent, e.g. B. one weak alkaline solution, methylamine, thiourea or zinc and acetic acid. In general, the course is the hydrolysis depends somewhat on the structure of the dye residue and the residue or residues that through Hydrolysis should be removed. However, it has been shown that the hydrolysis agents described are quite generally for the hydrolysis of z. B. carbonate, oxalate and trifluoroacetate residues are suitable.

For example, in the preparation of the dye developer compounds used in the present invention when using developer compounds that consist of polyhydroxybenzene compounds, z. B. hydroquinone, the masking residues of carbonate residues or containing such residues masking residues exist, e.g. B. Carboalkoxy radicals or carbobenzoxy radicals, which are preferably Have 2 to 20 carbon atoms.

During the development process: n the indophenol dye developing agent compounds are added to the Insoluble areas in which silver halide evolution occurs. The unreacted indophenol dye developer compounds diffuse into an image receiving layer, ζ. 3. a mordant layer. At some point in time according to the figurative Exposure of the silver halide layer or layers can use the indophenol dye developing agent then brought into contact with an onium compound, creating the indophenol radical is converted into an onium indophenoxide residue, creating the desired change in color absorption is effected to produce highly effective dyes for the color system.

In the case of the photographic recording units according to the invention, the pressure is applied resilient containers during the development process brought the recording unit in such a position that when a pressure is applied on the container its contents are set free from the container and distributed in the recording unit will.

The image receiving layer of the recording unit can be arranged on a separate layer support which can be applied to the recording part after the exposure of the recording part. Recording materials and recording units of this type are disclosed, for example, in US Pat

ίο 33 62 819 known. The splittable container or containers are normally inserted into a recording unit during the development process Brought position that when pressure is applied by means of pressure-exerting members such. B. from in a camera housed pressure-exerting members, the container contents between the image receiving element and pouring the outer layer of the photosensitive part of the recording unit.

The image receiving layer can furthermore be a

be an integral part of the photosensitive recording part and between the support and the be arranged at the lowest light-sensitive silver halide emulsion layer. Recording materials of this type with a so-called integrated

Image-receiving layer and a light-sensitive negative part are, for example, made of. the US PS 3415 644 and can be used, for example, in cameras from BE-PS 7 18 553 and 7 18 554 known type.

The developing liquid for the development of such integrated recording units to which the image receiving part is permanently laminated onto the negative part, contains an opaque material Means or opacifiers, ζ. B. titanium dioxide or

3S soot. Such recording units preferably have so-called separating layers which separate the various emulsion layers and dye developer layers from one another.
As in Fig. 5, the indophenol dye developer compounds can be used in a particularly advantageous manner for the production of recording units which have an integrated image-receiving layer which is separated from the image-recording layers, ie the light-sensitive silver halide emulsion layers, by an opaque layer which is permeable to dye developer compounds. The image-recording silver halide emulsion layers are in contact with the dye developer compounds. During the development of the recording unit, the developing liquid is applied uniformly to the image-recording layers which are separated from the image-receiving layer by the opaque layer. The alkaline developing liquid can be introduced between the image-recording layers and a cover sheet or end piece. The developing liquid then penetrates the image-recording layers, whereby the dye-developing compounds in the developed areas lose their diffusibility and the diffusion of the dye-developing compounds in the undeveloped areas is initiated through the opaque layer into the image-receiving layer. By reacting the dye developer compounds with

an onium compound then produces the desired image dyes. Since recording units of this type cannot be exposed through the opaque layer, the exposure must be from the opposite

set ropes. In the case of recording units of this type, the existing ones allow Indophenol color developing agents provide exposure through the corresponding side, whereby they are in effective contact with the silver halide emulsion layer or layers and are in become non-diffusing in the developed areas, thereby avoiding detrimental strong color contamination will. Because the indophenol color developing agent is incorporated into the emulsion layers can be or can be placed between an emulsion layer and a light source, without a disruptive substantial light absorption takes place, using the inventive Color developer compounds, highly sensitive photographic recording materials or Recording units. starting from negative emulsions and diffusing dye image-forming substances.

A particularly advantageous color photographic recording material according to the invention thus consists of a support with an image-receiving layer and an opaque or light-impermeable layer arranged thereon and at least one image-recording layer with a cover sheet over the image-recording layer. Such a recording material enables a working or developing liquid to be applied uniformly to the side of the image-recording layer or layers which faces the side of the opaque layer b / w. facing away from the image receiving layer.

After the development process has been completed, the cover sheet or the final part can be placed on the photosensitive part remain, i.e. form a lamination product with it.

Fine color photographic recording unit According to the invention, different sensitive silver halide emulsion layers in different Arrangement included. However, the usual blue-sensitive silver halide emulsion layer is preferred the first layer with respect to the exposure side, followed by the green-sensitive silver halide emulsion layer and finally the red-sensitive silver halide emulsion layer. Optionally, one containing a yellow dye Layer or a Carey Lea silver layer between the blue sensitive and the green sensitive Silver halide emulsion layer must be present to prevent blue radiation from passing through the blue-sensitive Layer has reached to absorb or filter off. Of course, the selectively sensebilized can However, silver halide emulsion layers also in a different order on a layer support be arranged, d. i.e., the red-sensitive layer may, with respect to the exposure side, the be the first layer, followed by the green-sensitive and blue-sensitive silver halide emulsion layers connect, since dye developer compounds for the production of the recording materials can be used, which in contact with the sensitive layers does not have any significant radiation of the visible range of the radiation spectrum.

The indophenol dye developing compounds used in the present invention can be used to produce all colors or in combination with additional dye-developing agents for production of tri-color recording materials.

Dyestuffs and veal compounds. which, if applicable used together with the indophenol dye developer compounds used in the present invention can be, d. H. Compounds that are in the same molecule as both the chromophoric system of a dye as well as having a silver halide developing function are known and will be ίο For example described in the following USA patents: 29 83 606, 29 92 106, 30 47 386,

30 76 808. 30 76 820. 30 77 402. 3126 280, 3131061,

31 34 762, 31 34 765, 31 35 604, Jl 35 605, 31 35 606. 31 35 734, 31 41 772, 31 42 565, 33 62 819. 34 15 644, 34 15 645 and 34 15 646.

The dye developing agents used in the present invention are advantageously used in common alkaline media diffusing. You can therefore use the usual image transmission systems can be used in which the color developing agents are in contact with silver halide mufsion layers stand and in which the silver halide emulsion layers are exposed and therefore with a alkaline working fluid are developed, welehe permeates the silver halide emulsion layers and the layers containing the color developing agents and developed the exposed silver halide In the districts where the silver halide emulsion layers are developed, the added color developing agent becomes relatively non-diffusing compared to the remaining offset color developing agents, which image-wise into a Ability to diffuse image receiving layer, in which they can be stained. When in contact with a Onium salt. preferably in the image receiving layer is present itself or in a layer adjacent to it. become onium indophenoxide dye images generated.

In the color developer compounds of the specified In the formulas, the developer residue D is generally responsible for changes in diffusibility the offset color developing agent, d. i.e., in the event of oxidation by reaction with exposed Silver halide or an auxiliary developer compound, the developer residue D is usually oxidized in such a way that that a relatively immobile connection is obtained.

Such color developer compounds have proven to be particularly advantageous which correspond to the given formulas, in which D is a polyhydroxy-substituted aromatic silver halide developer residue, in particular a hydroquinone residue.

The invention enables, inter alia, the production of black-and-white or single-color systems with only a silver halide emulsion layer and a color developing agent containing the desired Color effect. However, the invention is of particular importance for subtractive Multicolor systems, for example three-color systems, e.g. B.

of the type already described, in which a blue-sensitive Emulsion layer in contact with a superposed, a yellow indophenol dye producing Indophenol color developing agent is in contact with a green sensitive emulsion layer with an offset, a purple-red indophynol dye providing color developing compound and a red-sensitive emulsion layer in contact with an offset, a hlnuimincn

Indophenol dye-providing developer compound stands.

The indophenol dye developer compounds used according to the invention can be used in such high concentrations in color photographic records nursgsmatcriaücn that after the Development of the recording material in the usual known manner achieves a desired high color density will. The most favorable concentrations in the individual case may be of the type used Developer compound and the structure of the recording material and the like.

The onium compounds used to carry out the method of the invention can either be soluble compounds that are in the form of a solution with the indophenol color developer compounds in Contact can be made or the onium compounds can be extremely molecular Acting compounds which are relatively insoluble in water and in at least one layer of a recording material can be accommodated according to the invention, for example in a mordant layer or image-receiving layer, where by reacting the indophenol ■ color developer compounds with the onium compounds onium indophenoxide and dye images.

According to an advantageous embodiment of the invention, the onium compounds are quaternary Ammonium compounds used.

In general, their organic radicals are directly attached to the nitrogen atom through single or double bonds, namely carbon-nitrogen bonds bound. Under "quaternary ammonium compounds" are to be understood here quite generally those compounds in which the nitrogen atom is a core atom of a heterocyclic nucleus, as are those compounds in which the 4 valences are separated by individual organic residues are saturated, e.g. B. alkyl radicals, in which case quaternary tetraalkylammonium compounds are present.

Typical quaternary ammonium compounds useful in practicing the process of the invention can be represented, for example, by the following structural formulas:

Examples of compounds of the formulas 1, 2 and 3 are Tetraälhylammoniumbromid, N - Äthylpyridiniumbromid, Ν, Ν-diethylpiperidinium bromide, ethylene-bis-pyridinium bromide. l-ethylpyridinium bromide.

-Phenäthyl ^ -picoliniumbromid, Tetraalkylammoniuniäaizc, CclyilrimclhyianiiiiuiiiunibiOinid, Pokalkylene Oxide - bis - quaternary ammonium salts, e.g. B. polyethylene oxide - bis - pyridinium perchlorate, and also the heterocyclic quaternary ammonium salts which form methylene bases, including 3 - methyl -2-ethylisoquinolinium bromide. 3 - methylisoquinolinium bromide, 3 - methylisoquinolinium methyl - ρ - toluenesulfonate, 1 - ethyl - 2 - methyl - 3 - phenethylbenzimidazolium bromide, 5,6-dichloro-1-ethyl-2-methyl-3- (3-suIfobutyl) benzimidazoIium betaine and the pyridinium salts, which are described in more detail below.

Others for carrying out the method of the invention suitable onium compounds are tertiary sulfonium and quaternary phosphonium compounds, especially those that can be represented by the following formulas:

(R) ₃ S ⁺ X
(R) ₄ P ⁺ X

RN ⁺ -RY
R.

45

(I)

(21

(3)

55

60

where each R is an organic radical. z. B. an alkyl, aralkyl or aryl radical and X is an anion, ζ. Β. a hydroxy, bromide, chloride or toluenesulfonal anion.

Examples of tertiary sulfonium and quaternaries useful in practicing the process of the invention Phosphonium compounds are Lauryldimethvlsulfoniutn - ρ - toluenesulfonate, nonyldimethylsulfonium-p-toluenesulfonate and octyldimethylsulfonium p - toluene sulfonate, butyldimethylsulfonium bromide, Triäthylsulfoniumbromid, Tetraäthylphosphoniumbromid, Diinethylsulfonium-p-toluenesuüonat, Dodecyldimethylsulfonium - ρ - toluene sulphonate, dccyldimethylsulphonium-p-toluene sulphonate and ethylene-hisoxymethyltriethylphosphonium bromide.

The onium compounds can be used in the form of the hydroxide or in the form of a salt. If the onium compounds are used in the form of salts, the anion can be derived from the remainder any acid. It should be noted, however, that if the anion is an iodide anion. this can possibly exert certain adverse effects on the emulsion layers, which is why in the Usually certain precautionary measures must be taken when in contact with such onium salts get through the emulsion layers before development is complete.

Particularly gate results are obtained when bromides are used as onium compounds will.

As particularly advantageous heterocyclic ammonium compounds that form methylene bases, the are diffusing in alkaline solutions, the compounds of the following formula have been found:

R R_,

where R is in each case an organic radical and Y is an ion, e.g. B. a hydroxy. Bromide-. Chloride or Toluenesulfonate anion. Z stands for the atoms that / ur Completion of a heterocyclic ring or nucleus are required.

R - N M - =

-C-CH ₃ R '

in which D means the completion of a heterocyclic ring of a quaternary ammo

l-Benzyl-2-picolinium bromide of the formula

CH ₂ Q ₁ H ₅

1 - (3-bromopropyl) -2-picolinium-p-toluenesulfonate,

1 - phenethyl-2-picolinium bromide, l-v-phenylpropyl-2-picolinium bromide, 2,4-dimethyl-1-phenethylpyridinium bromide, 2,6-dimethyl-1-phenethylpyridinium bromide, 5-ethyl-2-methyl-1-phenethylpyridinium bromide, 2-ethyl-1-phenethylpyridinium bromide, 1- [3- (N-pyridinium bromide) propyl] -2-picoinium-p-toiuoisulfonate

C ₃ He- ^ O

P'Tss.

Anhydro- 1- (4-sulfobutyl) -2-picolinium hydroxide

C ₄ I! "SO,

nium compound having one or more reactive methyl groups of the formula —CH ₂ R 'in one or more ring positions, with the proviso that the other ring positions may or may not be substituted, e.g. B. the atoms required to complete a pyiidine, quinoun, benzoquinoline, benzoxazole, benzoselenazole, thiazole, benzothiazole, naphthothidzole, benzimidazole or isoquinoline ring, η = 0 or 1, R an optionally substituted alkyl. , ίο aryl or aralkyl radical of the benzene series, the alkyl radicals preferably having 1 to 4 carbon atoms, R 'is a hydrogen atom or one of the radicals represented by R and X is a hydroxyl radical or an acid anion, e.g. B. a bromide anion or an anion of the formulas CH ₃ CO ₄ - or

One or more of these can quatermire Ammonium compounds are used, optionally also in combination with onium compounds of the formulas 1, 2, 3, 4 or 5. They can advantageously be in the developing liquid, in the recording material or in both can be applied.

Typical onium salts which can be used advantageously and diffusing methylene phases form, are

"- Picoline-Zi-naphthoylmethyl bromide

1 - β - phenylcarbamoyloxyethyl - 2 - picolinium bromide

-CH ₃ · Br "

C ₂ H ₄ OCONHC ₆ H ₅

l-methyl-l-picolinium-p-toluenesulfonate,

1 - phenethyl-2,4,6-trimethylpyridinium bromide,

l-phenethyl-4-n-propylpyridinium bromide,

4-7-hydroxypropyl-1-phenethylpyridinium-

bromide and
1 -n-heptyl-2-picolinium bromide.

OH

According to a particularly advantageous embodiment of the invention, the image dyes are by means of a polymer, e.g. B. pickled a polymer with onium residues. Typical suitable mordants this The type are vinylpyridinium compounds, such as are known, for example, from US Pat. No. 2,484,430 are, furthermore, polymers with quaternary ammonium residues, as they are, for example, in the USA patents 36 25 694, 36 39 357, 34 88 706 and 35 57 006 and the Belgian patent 7 29 202 will.

The pickling agent can advantageously also consist of a so-called onium coacervate pickling agent, as is known, for example, from US Pat. No. 3,271,147.

In the F i g. 4 to 6 is a particularly advantageous recording material according to the invention in form a photographic recording unit shown schematically, the individual parts from which the recording unit is constructed are shown enlarged for the sake of clarity.

As can be seen from FIG. 4, the recording unit 10 has a splittable container which is arranged transversely to a leading edge of the photosensitive laminate and by binding elements 30 is being held. These binding elements can be made of a pressure-sensitive tape or the like. which covers the corresponding edges of the laminate. The other edges dos light sensitive Laminates are sealed together, either directly or leaving a space free to prevent developing liquid from dei during and after the development process Recording unit can leak after the splittable container 11 has been broken open

which can be done by means of pressure-exerting members 36.

In the case of the in FIG. 5, it is a unit of the photographic recording unit which has not yet been developed, d. H. a unit, di <not yet through the pressure-exerting members 3 < was conducted. The recording unit 10 in turn has a splittable container 11 with a alkaline developing liquid 12. soft time

Revealing opacifiers or opacifying MiHeI. In addition, the recording unit consists of a transparent layer support 15, onto which are: an image receiving layer 16 which is an onium compound contains or is in contact with an onium compound, furthermore an opaque reflective Layer 17, a red sensitive silver halide emulsion layer 18 coated with a cyan image dye producing dye developer sees in contact, an intermediate layer 19, a green sensitive c Silver halide emulsion layer 20 with a is in contact with a magenta image dye-providing dye developer, an intermediate layer 21 and a blue sensitive silver halide emulsion layer 22 coated with a yellow image dye supplying dye developer is in contact. The recording unit also has a transparent one Cover sheet or a transparent closure part 25, which is covered with a polymeric acid layer 24 and a so-called retardation layer composed of a polymer is coated.

The exposure of the recording unit takes place through the transparent cover sheet 25, which is preferably consists of a flexible layer material permeable to actinic radiation.

In Fig. 6 is a recording unit of the one shown in FIG. 5 shown after they durcii «Jen from the two pressure-exerting limbs 36 formed gap has been performed. Such members can be in a camera, for example of the type in which photographic recording units are not only exposed but simultaneously also be developed. As can be seen from FIG. 6 results, the pressure applying members 36 have the splittable container 11 split, resulting in a distribution of the alkaline developing liquid 12 with the opacifying agent between the retardation layer 23 composed of a polymer and the blue-sensitive silver halide emulsion layer 22 led.

After the development and image transfer have been carried out, a positive, laterally correct image can be obtained view through the transparent substrate 15.

The structural integrity of the photosensitive laminate can be, at least in part, by the adhesive characteristics are maintained between the individual layers of the recording unit will. The adhesion between the retardation layer 23 made of a polymer and the underlying layer 22, however, is less than the adhesion of the other surfaces or intermediate surfaces to each other, to ensure the distribution of the developing liquid 12 between the layers 22 and 23 to facilitate.

A photographic recording unit according to the invention can be produced by assembling the individual Components are produced in an atmosphere that has a sub-atmospheric pressure and by closing the photosensitive part of the recording unit with the transparent one Cover sheet to the left of the edges of the light-sensitive part to prevent air from entering. Of the Exclusion of air between the transparent cover sheet and the photosensitive part of the recording unit is desirable because it avoids the developing liquid Picks up air bubbles, which would lead to discontinuities in the positive image to be produced.

Details relating to the manufacture of photographic recording units of this type and the Ensuring a uniform distribution of the developing liquid between two layers, are described in more detail in Belgian patent 7 11 897.

A photographic recording unit according to the invention may further be a so-called Contain fluid trap on the side that the side

ίο is the opposite of that from which the development fluid is introduced into the recording unit to collect excess developing liquid and prevent it from leaking out of the recording unit. Such a liquid wedge trap can also have the function of an air trap if air should be present. The use of such liquid traps is for example from Belgian patent 7 11 899 known.

A photographic recording unit according to the invention can further be used, for example, according to that known from the Belgian patent 7 11 898 Procedures are being developed in which two sets of pressure-exerting rollers or rollers are used to do this may be used, any air between the transparent cover sheet and the photosensitive recording member keep away and a particularly uniform distribution of the developing liquid between the cover sheet and the recording part to facilitate. The transparent cover sheet can also be used of the recording unit have flares along its edges, as for example from the Belgian patent 7 11 898 are known to / u ensure that a: uniform distribution of the developing liquid and the photosensitive Part of the recording unit takes place.

If any water that is still present is to be removed after the development process has been carried out, then this is done by using recording units with a drying layer which Absorb water or by creating an access to the atmosphere, so that the existing Water can evaporate, which can be achieved, for example, that pcrmeable for water Cover sheets can be used or for water-permeable film supports or by being allows the water to escape through liquid traps of the type already described.

The splittable containers can for example from a splittable container of the one from the I'SA. patents 25 43 181, 26 34 886, 26 53 732, 27 23 051, 30 56 492, 30 56 491 or 3152515 known Type exist. Advantageously, such splittable containers consist of a for Liquids and air impermeable sheet material that once formed two Container walls is folded and in which the other side edges are sealed together j with the formation of a container in which the development liquid 12 is contained with an opacifier (see FIG. 5). The sealing of the long edge 35 is made weaker than the sealing of the other edges, so that they are easy is split under the action of hydraulic pressure, so that the contents of the container escape can.

As can be seen from the F i ü. 4 and 5 is the container 11 firmly arranged in the Auffcichnuncscinhcut

and extends transversely to a leading edge of the photosensitive laminate so that when pressure is applied emptying of the container in one direction between that made of a polymer Delay layer 23 of the transparent cover sheet 25 and the underlying layer 22 takes place. As can be seen from FIG. 5 results, the weakly formed longitudinal seal 35 is on the intermediate surface between the layers 22 and 23 directed to the emptying of the container in the desired manner to facilitate.

A photographic recording unit according to the invention can, as shown in Fig. 5, are exposed through the transparent cover sheet 25 through. After the exposure, the film unit becomes 10 developed by, for. B. in a camera by the two pressure-exerting members 36 formed gap is passed through, whereby the splittable container is broken open, namely along the sealing edge 35, thereby distributing the alkaline developing liquid 12 with an opacifier between layers 23 and 24 of film unit 10. The alkaline developing liquid then penetrates the silver halide emulsion layers 22, 20 and 18 and initiates the imagewise development of the silver halide. Included at least some of the mobile yellow, magenta and blue-green image dyes which are present in imagewise distribution, develop developing compounds transferred by diffusion into the image-receiving layer 16, a positive dye image, is preferably obtained on contact with an onium compound. The one obtained in this way positive laterally correct image can be reflected through the transparent layer support 15 on the opaque Background layer 17 can be viewed. Since the image receiving layer is not from the negative part of the recording unit needs to be stripped off, the entire recording unit can after performing stay together during the development process.

The dyes used according to the invention; developer compounds allow exposure of the recording unit through the transparent Cover sheet 25 and still allow effective contact with the silver halide emulsion layers, so that the dye developing agents in the developed areas cannot be made developable, thereby causing color contamination be prevented.

The dye developing agents can be incorporated in the emulsion layers themselves or between these emulsion layers and the light source, without harmful light absorption, so that by using the dye developing agent, the manufacture is more highly sensitive photographic recording materials and recording units based on negative emulsions is made possible.

In a photographic recording material or in a photographic recording unit According to the invention, the individual silver halide emulsion layers containing a color developing agent contain or the individual silver halide emulsion layers which are associated with an adjacent The layer with a color developing agent is in contact with each other, i.e., with other silver halide emulsion layers be separated from one another by intermediate layers in the negative part of a recording unit, e.g. B. by layers of gelatine, Calcium alginate or other substances, as described, for example, in US Pat. No. 3,384,483 or polymeric substances, for example based on polyamides, such as those for example in the USA. Patent 34 21 892 or by layers of materials, such as those for example in French patent specification 20 28 236 and USA patents 29 92 104, 3043 692, 3044 873, 30 61428, 30 69 263, 30 69 264, 3121011 and 34 27 158.

Advantageously, the silver halide emulsion layers have of the recording materials according to the invention have a layer thickness of about 0.6 to 6 microns, the emulsion layers advantageously being composed of gelatin-silver halide emulsion layers can exist. The compounds which provide the image dyes can advantageously in a polymeric binder permeable to aqueous alkaline solutions, e.g. B. gelatin be dispersed and in the form of separate layers about 1 to 7 microns thick. Has a recording material or a recording unit according to the invention for alkaline solutions permeable Intermediate layers on, e.g. B. gelatin interlayers, these interlayers are more advantageous A thickness of 1 to 5 microns can optionally be used, however, depending on the specified thickness ratios be deviated. In addition to gelatin, the individual layers of the recording materials can be used to prepare and recording materials the usual other known hydrophilic binders can be used, both of natural and synthetic origin, i. H. Proteins, cellulose derivatives, Polysaccharides, e.g. B. dextran, gum arabic and the like, and on the other hand such synthetic ones polymeric substances such as water-soluble polyvinyl compounds, e.g. B. polyvinyl pyrrolidone and acrylamide polymers.

The photographic emulsion layers and other layers of a photographic recording material or a photographic recording unit according to the invention can furthermore alone or in combination with a hydrophilic, water-permeable colloid other synthetic substances included, e.g. B. dispersed polyvinyl compounds, for example in latex form, in particular those which increase the dimensional stability of the photographic material.

Typical polymers of this type are, for example : those of U.S. Patents 3142 568, 3193 386, 3062 674, 32 20 844, 32 87 289 and 3411911 known polymers. As special The water-insoluble polymers of alkyl acrylates and alkyl methacrylates have proven to be effective, Acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates and also those that have crosslinking centers that cause hardening and finally those which have recurring sulfobetain units, such as, for example from Canadian Patent 7,74054 are known.

A wide variety of substances can be used to produce the image-receiving layers, insofar as they are used these exercise a mordant function or to fix the transferred dye images in some other way capital. The structure of the image receiving layer depends in each individual case on the dye to be pickled

509 584/373

picture from. According to one embodiment of the invention, the image-receiving layer can consist of a polyvinylpyridine mordant exist or contain one. Those using a polyvinylpyridine mordant Mordant dyes, however, are different from those made using an onium mordant are generated, namely, that they are from the mordant layer with repeated washing can be removed. By using a pH reducing layer in a recording unit the stability of the transmitted image can be increased. It has proven to be beneficial have been shown to use such pH-reducing layers which reduce the pH of the image layer from about 13 or 14 to at least 11 and preferably to 5 to 8 within a short period of time after exposure to the developing solution. To prepare the For example, so-called polymeric acids can be used to reduce the pH value. as described, for example, in U.S. Patent No. 33 62 819 will. Such polymeric acids reduce the pH of a recording unit of development and interrupt or terminate the development process and practically prevent another dye transfer to stabilize the transferred dye image. In advantageous Polymers can be used to produce the pH-reducing layer, which have acidic groups, e.g. B. carboxylic acid groups and sulfonic acid groups, which with alkali metals, z. B. sodium and potassium or with organic bases, especially quaternary ammonium bases, z. B. tetramethylammonium hydroxide, able to form salts.

The polymers used to produce the layers which reduce the pH can also be used have so-called groups forming potential acid groups, e.g. B. anhydride or lactone groups or other groups which are able to form bases by reaction. As particularly beneficial the use of polymeric acids which have free carboxyl groups has been found and which are insoluble in water in the free acid form and the water-soluble sodium and / or potassium salts form. Examples of typical suitable polymeric acids are the dibasic acid half-ester derivatives the cellulose having free carboxyl groups, e.g. B. Cllulose acetate hydrogen phthalate. Cellulose acetate hydrogen glutarate, Cellulose acetate hydrogen succinate, ethyl cellulose hydrogen succinate, ethyl cellulose acetate hydrogen succinate, cellulose acetate succinate hydrogen phthalate as well as ether and ester derivatives of cellulose, modified with sulfoanhydrides, z. B. with ortho-sulfobenzoic anhydride and also polystyrene sulfonic acid, carboxymethyl cellulose. Polyvinyl hydrogen phthalate, Polyvinyl acetate hydrogen phthalate. Polyacrylic acid. Acetals of polyvinyl alcohols with carboxy- or sulfo-substituted aldehydes, e.g. B. o-, m- or p-benzaldehyde sulfonic acid or a carboxylic acid. Partial esters of ethylene maleic anhydride copolymers, Partial esters of methyl vinyl ether - maleic anhydride copolymers and the like. Layers also solid monomeric acidic substances are used, for example palmitic acid, oxalic acid, Sebacic acid, hydrocinnamic acid. Metanilic acid, p-toluenesulfonic acid and benzene disulfonic acid. Further, Typical substances suitable for producing the layers which reduce the pH are, for example from the USA patents 34 22 075 and 26 35 048 known.

It has proven to be expedient to place the layers reducing the pH value in a thickness of about 0.0076 to 0.038 mm to produce and they in the Ernpfangstei! of the recording unit between de * m Support and the image receiving layer on the

ίο to accommodate cover sheet or final section. on the other hand however, the layers can also be used in a wide variety of other locations on a recording material or a recording unit according to the invention, as long as they only have the perform the desired pH-reducing function.

Advantageously, an inert retarding or delaying layer can be placed over the pH-reducing layer Spacer layer are arranged, which has the task of controlling the pH reduction or as a function of the rate at which the alkali passes through this inert layer diffused. Such delay or control layers can also be effectively used for this purpose are, oxidizing substances in a layer adjacent to the image receiving layer, in which oxidizing To isolate substances after the alkali breakthrough of the delay or control layer. Such control or delay layers can, for example, made of gelatin, polyvinyl alcohol or other substances, as described, for example, in US Pat. No. 3,455,686 be. Such a control or delay layer can also advantageously be compensate for different reaction rates over a wide temperature range, e.g. Legs Prevent the pH value from being lowered too early if the development fluids takes place at temperatures above room temperature

door, for example at temperatures of 35 to 37.8 ° C. Such are advantageous Retardation or control layers about 0.00254 to about 0.018 mm thick. Particularly beneficial results can then be obtained if the control or retardation layer consists of a hydrolyzable Polymers is built up or from a mixture of such polymers, which slowly be hydrolyzed by the developing liquid. Examples of such hydrolyzable polymers are Polyvinyl acetate, polyamides and cellulose esters.

Those used for developing the exposed recording materials and recording units Alkaline developing solutions can be prepared from conventional aqueous solutions of an alkaline compound exist, e.g. B. Solutions of Sodium Hydroxide. Sodium carbonate or an amine, e.g. B. of diethylamine, wherein the developing solutions preferably have a pH of above 12 and the] further preferably contain a so-called auxiliary developer connection.

The developing solutions preferably also contain a viscosity-increasing compound, z. B. a high molecular weight polymer, e.g. B. a water-soluble ether, which is opposite to alkaline solutions is inert, e.g. B. Hydroxyethyl cellulose or an alkali metal salt of carboxymethyl cellulose, e.g. B. the sodium salt the carboxymethyl cellulose. Such viscosity-increasing substances can advantageously be used

Compounds in the developing liquid in concentrations of from about 1 to about 5 percent by weight, based on the weight of the solution. The viscosity-increasing compounds are preferred used in concentrations such that the developing liquids have a viscosity of about 100 cP to about 20,000 ocP. If necessary, the developing liquid can also contain an adhesive or an adhesive compound can be added, for example, if an increased Adhesion of the transparent cover sheet or transparent closure part to the light-sensitive Part of a recording unit after its development is to be effected.

Those for developing photographic recording materials and recording units Alkaline developing solutions used in accordance with the invention can thus provide an auxiliary developing agent or contain a compound that accelerates the development process that is not Structural formula D - (SID) corresponds.

Typical auxiliary developer compounds (reducing agents) that can be used for development, are for example p-methylaminophenol, 2,4-diaminophenol, p-Benzylaminophenol, hydroquinone, tolu hydroquinone, phenyl hydroquinone and 4-methylphenyl hydroquinone. Furthermore, various auxiliary developing compounds and compounds accelerating the development process can be used of the type known from U.S. Patent 3,039,869 can be used. Such connections however, can be used not only in the developing liquid, but rather also at least partially in one or more layers of a photographic recording unit the invention. '. B. one or more silver halide emulsion layers. Layers housing the dye developing agent or interlayers or in the image-receiving layer. They can advantageously be used in the layers of the photosensitive part of a recording unit be accommodated according to the invention.

The alkaline developing liquids used for development may further contain a desensitizing agent, e.g. B. Methylene Blue or a heterocyclic compound substituted by one or more nitro radicals, 4,4'-bipyridinium salts and the like to ensure that the recording material or the recording unit no further exposure after removal from the camera.

Although the alkaline developing liquid is preferably in a splittable container of the type described Type, thereby introducing the developing liquid into a recording unit between the transparent end part and the photosensitive or photosensitive Element is facilitated, but other means can be used to make the developing liquid to be inserted into the recording unit. For example, the developing liquid can also with the help of communicating limbs, similar to hypodermic syringes, either in a Camera are arranged or a camera cartridge are inserted into the recording unit, d. H. for example by a method as described in the SA patent 33 52 674.

As already stated, can be used to develop a recording material or a recording unit According to the invention used developing liquid also an opacifier or

5 opacifying agents included. Typical opacifiers or opacifying agents are, for example Carbon black, barium sulfate, zinc oxide, barium stearate, silver flakes, silicates, aluminum oxide, zirconium oxide. Zirconium acetylacetate, sodium zirconium sulfate,

, o Kaolin, mica, titanium dioxide and organic dyes such as nigrosine or mixtures thereof. The concentration of opacifying agents or opacifying agents is so great that a further exposure of the silver halide emulsion layer or silver halide emulsion layers of a recording unit to radiation surrounding the unit, which can penetrate through the transparent cover sheet, after the development liquid has been distributed between the cover sheet or closure part and the one below Layer or the layers below it is avoided. For example, carbon black or titanium dioxide can be used to achieve sufficient haze or opacity if these substances are present in the developing liquid in concentrations of about 5 to 40 percent by weight. After the development liquid with the opacifier has been distributed in the recording unit, the development process can take place outside the camera in the presence of actinic radiation, since the silver halide emulsion layer or layers of the recording unit are protected from the incidence of radiation, on one side by the opaque opacifier and on the other side by the opaque layer which is permeable to alkaline solutions. Opaque end tapes or end strips can also be used to prevent actinic radiation from entering through the edges of the recording unit.
If a developing liquid containing titanium dioxide or another white pigment is used as the opacifier, it can be advantageous to use a pH-sensitive opacifying dye, e.g. B. Phthaleia. A clouding dye is to be understood as meaning dyes which are light-absorbing at the pH value at which an image is generated or colored and colorless or not light-absorbing at a lower pH value. For further details of such opaque dyes, reference is made to French patent specification 20 26 927.

Permeable, practically opaque for alkaline solutions. Light reflective layer of a photographic Recording unit according to the invention can also use a wide variety of opacifiers or

5f, opacifying agents, dispersed in a binder, provided that they have the desired effects cause. Particularly advantageous opaque light-reflecting layers have proven to be those which consist of white light reflecting layers, as these have an aesthetic point of view can provide a pleasing background upon which to view the transferred dye images and because such layers furthermore have the optical properties that are desirable for a reflection of incident radiation. Typical opacifiers or opacifiers Means for generating the light-reflecting layers are: titanium dioxide, barium sulfate, zinc oxide, barium

stearate, silver flakes, silicates, aluminum oxide, zirconium oxide, Zinc acetylacetate, sodium zirconium sulfate, Kaolin, mica or mixtures thereof in various concentrations, depending on the desired degree of opacity, the opaque making center! or opacity center! can do it in the usual known binders, the layers of yeasts which are permeable for alkaline solutions e.g. in gelatin, polyvinyl alcohol and the like Layers of optical brighteners are added, for example on stilbene, coumarin, triazine and / or oxazole base. Optionally, the opacifying or opacifying capacity of the Light-reflecting layer can be increased by adding dark-colored opacifiers to the layer be e.g. B. carbon black and / or nigrosine dyes. Another method for increasing the opacity capacity of the light-reflecting layers is to use in placing a separate opaque layer beneath this layer, e.g. B. a layer with soot or a nigrosine dye dispersed in a polymeric binder that is permeable to alkaline solutions, z. B. gelatin or polyvinyl alcohol. Such an opaque layer preferably has a density of at least 4 and preferably over 7 and is practically opaque or impermeable to ».. actinic radiation. The opaque layer can also optionally be coated with a developer trapping layer combined, if one is provided. The light reflective and opaque layers preferably have a layer thickness of 0.025 to 0.15 mm, it being the case that these layer thicknesses can be fallen below or exceeded, depending on the opacifier used and / or the degree the desired haze or opacity.

Those for making a photographic material or a recording unit according to the invention used transparent support or cover sheets or end pieces can consist of a wide variety of transparent materials, as long as these are not disadvantageous Effect on the photographic properties of the recording materials and recording units exercise and are dimensionally stable. Typical, door actinic radiation transmissive flexible sheet-shaped Materials that can be used can, for example, from films made of cellulose nitrate, Cellulose acetate, polyvinyl acetate, polystyrene, polyethylene terephthalate. Polycarbonates, poly-u-olefins, e.g. B. polyethylene or polypropylene and others Polymers as well as made of glass. The transparent cover sheet or the transparent end part advantageously has a thickness of about 0.05 to 0.15 mm. If necessary, it can be one UV absorbers included for exposure control. If necessary, such a cover sheet or end part further have a so-called adhesive layer, which is formed by the developing liquid is activated and the adhesion of the cover sheet or the end part on the photosensitive Reinforced part of the recording unit.

If the recording materials or recording units according to the invention are transparent Layer support on, they can consist of any material from which the cover sheets or End parts are made. The layer support can optionally also contain a UV absorber; to protect the generated dye images from fading by ultraviolet light.

Advantageously, the recording materials can be used to produce the photosensitive layers and recording units according to the invention use a wide variety of silver halides e.g., silver chloride, silver bromide, silver bromide iodide, silver chloride bromide iodide and the like. or mixtures thereof. Those for the production of the recording materials and recording units Silver halide emulsions used can consist of coarse-grain or fine-grain emulsions and manufactured by customary known methods. This means that the Emulsions, for example, so-called single enema emulsions or double enema emulsions, z. B. Lippmann emulsions or ammoniacal emulsions, in the presence of thiocyanates or Thioether-ripened emulsions, such as those in U.S. Patents 22 22 264, 33 20 069 or 32 71 157 described, can act. For the production of the recording materials and Recording units can also be so-called. Surface-forming emulsions are used and also so-called internal-forming emulsions, such as they are described, for example, in U.S. Patents 25 92 250, 32 06 313 and 34 47 927. The emulsions can also be emulsions with regular silver halide grains act as they are, for example, by Klein and M ο i sar r in the journal J. Phot. May be. Vol. 12, No. 5, 1964, pp. 242-251. Possibly Mixtures of surface emulsions and internal emulsions can also be used, how it z. B. from US Pat. No. 2,996,382 is known.

Preferably, for the production of the recording materials and recording units according to the invention uses negative-type emulsions. However, direct-positive emulsions can also be used be used. Typical direct positive emulsions used in the production of recording materials and recording units according to the invention can be used are, for example from U.S. Patents 2184 013, 25 41 472, 33 67 778, 35 01 307, 25 63 785, 24 56 953 and 28 61 885, also British patent specification 7 23 019 and Belgian patent specification 7 80 538, 7 80 540, 7 85 065 and 7 84 945 as well as the USA patent application 1 54 154 known.

When using the recording materials and recording units according to the invention, leave them positive photographic images are obtained by pickling the color developing agent diffused into the image receiving layer received, d. H. by diffusion of the dye developer compounds which are not in the photosensitive recording material immobilized or remained non-diffusing. It should be noted that, however, also z. B. the photosensitive part of a recording unit has an image record which can be used is. For example, the mobile or diffusible dye developer compounds washed off after exposure to give a negative image. According to another Embodiment of the invention can be the silver halide emulsion layer or can the silver halo

genide emulsion layers are selected so that in the photosensitive part of a recording unit a positive image is obtained.

In the following, the preparation of some indophenol dye developer compounds which can be used according to the invention will first be described are described in more detail.

1. Preparation of the indophenol dye developer compositions which can be used in accordance with the invention

Preparation Example 1 A. Preparation of Intermediate I-A

OCOOC ₂ H ₃

SOCl,

CH ₁ COOH

2. H ₂ N OCH ₁

OCOOC ₂ H ₅

(D

A suspension of 2.4 g (0.04 mol) of compound 1 in 50 ml of dry benzene was used for 30 minutes long with 10 ml of thionyl chloride at reflux temperature heated. Then the benzene was removed, leaving an oil with 10.8 g (0, ö4 mol) of the Compound 2 and 5 ml of Ν, Ν-dimethylaniline in the form an acetone solution was treated. The mixture was left to stand overnight, followed by the solvent removed and the residue was recrystallized from acetonitrile. That way were 12.4 g of the solid intermediate compound 1-A having a melting point of 163 to 167 ° C. were obtained. By Thin layer chromatography determined that the reaction product consisted of a compound. A recorded infrared spectrum agreed with the results of thin-layer chromatography match.

B. The Preparation of Intermediate I-B

A suspension of 8.4 g (0.015 mol) of the intermediate compound 1-A in 300 ml of dimethoxyethane was admixed with 0.58 g (0.015 mol) of an NaH dispersion. After stirring for 30 minutes, 5.9 g (0.015 mol) of the following compound 4 were added:

COCH ₂ CONH

(2)

The mixture was left to stand overnight. The solvent was then removed, whereby an oil remained which was dissolved in chloroform. The solution was filtered through a silica gel filtered. After removing the solvent, the residue was obtained from a benzene-cyclohexane mixture recrystallized. Thus 3 g of Intermediate I-B was obtained. By thin layer chromatography it was found that the reaction product consisted of a compound. to An infrared spectrum produced the same results.

C. Preparation of Compound I, d. H. one, one

delivering yellow dye
Indophanol dyes develop a binder compound

A solution of 10 g (0.012 mol) of the intermediate I-B in 200 ml of methanol was added for 1 hour in a nitrogen atmosphere with 2.8 g (0.05 mol) Potassium hydroxide, dissolved in water, heated to reflux temperature. After the reaction mixture had cooled, it was acidified with acetic acid and then extracted with ether. The ether extract was concentrated, whereupon the remaining oil was recrystallized from a benzene-ethyl acetate-cyclohexane mixture. It was 1 g of the compound I. obtain. The reaction product was found to be a compound by thin layer chromatography duration. A nuclear magnetic resonance analysis and the recording of an infrared spectrum agreed with the results of thin layer chromatography.

Preparation Example 2 Preparation of a cyan dye-providing dye developing compound

N-SO ₁

45

(4)

OCOOC ₂ H ₅

CH ₂ COOH

1. SOCl,

OH

OCOOC ₂ H ₅

(U

A solution of compound 1 in dry tetrahydrofuran was treated with a mixture of thionyl chloride and NN-dimethylformamide in dry II ₂ N-

NHCOC ₃ F,

Benzene heated for 30 minutes. The solvent was then removed under reduced pressure, possibly the corresponding acid chloride with a

Melting point of 50 to 53 ^C C remained. The acid chloride was then dissolved in dry dioxane and the solution was added to a mixture of compound 2 and quinoline in dry dioxane. After standing at room temperature, the deposited precipitate was filtered off and recrystallized from acetonitrile. The intermediate compound A with a melting point of 198 to 200 "C was obtained.

A solution of Intermediate A in tetrahydrofuran was prepared with the compound of the following Offset formula:

N-Cl

added, whereupon the deposited precipitate is filtered off and was dissolved in chloroform.

The solution obtained was chromatographed using silica gel. wherein "a dye developing agent having the following structural formula was obtained:

OCOOCH

₂ H ₅

: O -CH ₂ CONH

OcOOC ₂ H ₃

'V-NHCOC ₃ F ₇

Br-

Br

Br

whereupon a solution of sodium bicarbonate in water and methyl alcohol was added and the whole thing Was stirred for 1 hour. Then water became OH

The melting point of the compound was 136 to 137 C.

Preparation Example 3 Preparation of a magenta dye-providing dye developer compound

OCOOC ₂ H ₅
0VCH ₂ COOH

^SOCl2

I0

Η, Ν- ^ Vci

OCOOC ₂ H ₅

(D

A suspension of compound 1 in dry benzene was made with thionyl chloride and N.N-dimethylformamide Heated to reflux temperature for 20 minutes. Thereupon the solvent became at reduced The pressure was removed, whereupon the residue was dissolved in acetic acid. The solution became too added to a solution of the compound 2 in acetic acid containing sodium acetate. the The mixture was stirred for 2 hours and then left to stand overnight. Thereupon was poured them into water. After neutralization with sodium bicarbonate, the deposited solid precipitate became filtered off and recrystallized from ethyl acetate. The intermediate compound A was with obtained a melting point of 135 to 136 ° C.

A solution of intermediate A in ethyl acetate and tetrahydrofuran was made with sodium bicarbonate treated, whereupon a compound of the following formula was added:

N-Cl

Br

Br

This was followed by stirring for 1 hour. Damn water was added, was filtered ilter whereupon the mixture through a celite ^C. The filtrate was extracted with chloroform. After washing with water, the organic layer was separated, dried and concentrated under reduced pressure. The residue was chromatographed on silica gel. Intermediate B was thus obtained.

A solution of the intermediate compound B in tetrahydrofuran and pyridine was treated with a 3% igeri Sodium carbonate solution is added and the whole is carried out for 5 hours in a nitrogen atmosphere Reflux temperature was heated. After cooling, the solution was dissolved in a dilute acetic acid solution given, whereupon the deposited precipitate was filtered off. In this way, the Compound 2 received.

Offset dye useful in the invention Developer connections can also be made by a method as shown below Preparation example 4 is described in more detail, ir the oxichromogcnc compounds of the in the German see patent application P 22 60 203.5 of the type described to be implemented further.

Production example 4

The oxichromogenic compound 4- (3,5-Dichlorc 4 - hydroxyanilino) - 2 - [5 - (2,5 - dihydroxyphenyl 'pentanoylamido] - 5 - (4 - pentoxybenzamido) - phenc (1.449 g, 2.11 ■ 10 " ³ mol), produced as described in the deul patent application P 22 60 203.5

I was dissolved in 300 ml of a mixture of 80 percent by volume acetonitrile and 20 percent by volume Ν, Ν-dimethylformamide, whereupon enough sodium perchlorate was added to the solution that the solution plus sodium perchlorate was 0.1 molar. The solution was then oxidized by controlled potential electrolysis in a two-chamber cell using a potentiostat and platinum electrode at a potential of + 0.55 volts until the current had dropped to 10% of its original value. The progress of the reaction was monitored by occasionally recording the current-voltage curve. After 375.1 coulombs (2.05 electrons / molecule) had been consumed, the first oxidation stage (E ₁ ) of the leuco dye had decreased to about 5% of the original level, whereas the second stage (E ₂ ) had retained its original level. The resulting red solution was filtered, and water was added dropwise to cause the reaction product to precipitate. The red solid precipitate was filtered off, washed several times with water and dried under reduced pressure.

In this way, 1.4 g of reaction product was obtained in a yield of practically 100%. The current efficiency was 100%. After recrystallization from ethanol, the compound IV with a melting point of 200 to 201 ⁰ C was obtained.

Compound IV O

(CH ₂ J ₄ -CONH

NHCO

OC ₅ H ₁₁

OH

Production example 5

The oxichromogenic compound 4- (3,5-dichloro-4-hydroxyanilino) -3-3 - [5 - (2,5-dihydroxyphenyl) -pentanoylamido] phenylcarbamoyl -1 - phenyl - 2 - pyrazolin-5-one, prepared as in the German patent application P 22 60 202.4 described, was for the purpose of removing the masking residues on the developer residue subjected to hydrogenolysis. Subsequently, the reaction product became an air oxidation subjected to a staggered color developing agent of the assumed, considered hereinafter Structural formula was obtained:

Compound V

(CH ₂ ) ₄ -CONH NN-QH ₅

The following examples are intended to further illustrate the invention.

II. Examples

example 1

This example illustrates the property of a dye developing compound useful in the present invention in contact with a pickling agent, e.g. B. an organic onium compound, a spectral To be subject to absorption shift.

A. A layer support with a gelatin layer of 250 mg gelatin and 70 mg of the compound I per 0.0929 m ^{2 support area} became OH after drying

evaluated spectrophotometrically. The spectrophotometric absorption profile 1 of compound I corresponds to curve A in FIG. 2.

B. A sample of the described material was immersed in a mordant solution of the following for 1 minute specified composition submerged:

Hexadecyltrimethylammonium

bromide 5 g

K, HPO ₄ (0.5M) 430 ml

KH ₂ PO ₄ (1.5M) 70ml

Topped up with water to 11

pH = 7.0

37 38

After removal from the solution, the test _R. 14th

ling dried and spectrophotometric again "

evaluated. The absorption profile of compound I A. A section of a recording material as described in the test specimen post-treated corresponds to curve B, game 3, was uniformly shown in FIG. 2. 5 flash exposed. A second section of the record

A comparison of curves A and B in FIG. 2 shows the imaging material remained unexposed. The examinee was

that the compound was originally in intimate contact with a for 30 seconds

sorption and, after the aftertreatment, a high layer of mordant with a coacervat mordant such as

Has absorption for blue light. Brought described in Example 2, namely in

... »10 presence of a viscous developing liquid

^{Example 2} 20g sodium hydroxide, 25g hydroxyethyl cellulose

This example illustrates the transfer of one and 0.75 g of l-PhenyM-methyl- ^ hydroxymethyl-

according to the invention usable dye developer 3-pyrazolidone per liter of aqueous solution,

connection in an image receiving layer and after separation of the test specimen from the image

When a stained dye was produced in the image-receiving layer, the latter showed a dense yellow color

reception shift. Dye layer in the section which during

A section of the transfer process described in Example 1 under A is the one that is not exposed

Nine material was opposed in the intimate portion of the recording material for 30 seconds.

Brought into contact with a mordant layer composed of The image-receiving element was treated for 3 minutes

a coacervate of Nn-hexadecyl-N-morpholi- ₂₀ wash without any noticeable change

sodium ethosulphate and methyl-tri-n-dodecyla.-nmonium- perceivable in the appearance of the yellow dye layer

p-toluenesulfonate was built up. The contact was made bar.

in the presence of a viscous liquid developing agent B. The procedure described in A was again the following composition given by: derholt, but Vv and a time development, α ™ a ma ² S was used liquid, which only from 40 g

Potassium hydroxide M g potassium hydroxide and 30 g hydroxyethyl cellulose per

_{Hydroxyethyl cellulose} 30 g Utn ^ _be | * present case

Topped up with water at 11 _{(each auxiliary developer} compound was omitted. In

After separation of the gelatin layer from this case, a yellow dye layer appeared

The image receiving layer left a 30 in both sections of the image receiving material in the latter. the end

uniform, dense distribution of the yellow dye - this experiment shows that the auxiliary developer -

fabric. The image receiving layer undergoes an immobilization reaction for 3 minutes,

washed for a long time without any change in the. .

The appearance of the yellow dye layer can be noted in Example 5

could. B is ρ ie 1 3 35 ^ ' ^e offset dye developer compound IV

A multilayer color photographic was tested as follows:,. ...,

Recording material produced in that on. ^{A. A} _f ^{u a, en} Celluloseacetatschichttrager were

a support the following layers, listed ^{in de} _f ^ order, the following layers

(the following concentration data are plotted (the concentration data relate to

each relate to a layer support area of *> ^W ' ^e _{Q of} ^the ₂ T ^{JCWeils to a} layer support area of

0.0929 m ² ): u, wm).

1. a layer of 250mg gelatin, 70mg of the ^L

Compound 1 and 70 mg of diethyl lauramide,. JF ?? ^ JP ^ l ^^^:, -

2. a silver halide emulsion _{layer of 250 mg of 45} ^{Z a} gelatin top layer of 80 mg of gelatin.

Gelatin and 200 mg silver, B. Furthermore, a photographic recording was

3. a layer of 80 mg gelatin. Drawing material produced in that on a A section of the recording ma cellulose acetate layer support produced in the following

terials were exposed through a test object with graduated g ^ J ^^ * ™! ™, ^ ^indicated density levels and then applied in reverse order 5 °:
waiting for a viscous developing liquid of the composition specified in the first a layer of 125 mg gelatin, 75 mg diethyl 30 secundauramide and 50 mg of the compound IV,
which was brought into contact for a long time with an image-receiving layer 2. a layer of a monodisperse silver which contained the pickling bromide emulsion described in Example 2 with 100 mg of silver and 10 mg of 1-phase agent. ⁵⁵ nyl-3-pyrazolidone and 100 mg gelatin and

After separating the recording material from 3. a gelatin top layer of 80 mg gelatin,
the image receiving layer was a well _in ^ latter: nevertheless _{Dag fcej syllable} rhalo _g enid containing material mertes positive yellow image of the photographed ^^ _{jn dnem Spektrophotomeler} analyzed. ErTestobject visible. «..- ..,. ο,. 60 a value at 590 nm was averaged with a

The EntwicKlungsflussigkeit used had folic _{D value yon O55> wi = by the curve> 4}

The following composition: _F { 3 is _shown .

Sodium hydroxide 20 g A section of which does not contain silver halide-

l-Phenyl- ^ methyl- ^ hydroxymethyl- the test material was in a 5% aqueous

3-pyrazolidone 0.75 g of a 65 methanolic solution of l-phenyl-3-pyrazolidone

Hydroxyethyl cellulose 25 g dipped. The immersion time was 5 minutes. Included

When made up to 11 with water, the recording material was practically completely

pH = 13.7 dig decolorized. A spectrophotometric absorption

39 40

tion curve of the treated material is that in colored photographic recording materials

F i g. 3 curve shown β. and recording units of the US patent

One section each of the untreated material, font 29 83 606 and the one from the Belgian patent and the documents 7 57 959 and 7 57 960 with the 1-phenyl-3-pyrazolidone solution and the in the Acted material was in contact with a picture-5 German patent application P 22 60 194.1 Beschrieempfangsblatt brought that suitable as a pickling agent N-n-octabene type.

decyltributylammonium bromide and in counter- It was a recording material with a rotwart the development-sensitive silver halide emulsion layer indicated below, one developed liquid: blue-sensitive silver halide emulsion layer ,, .. ,,.,. "ίο and a green-sensitive silver halide

^ aliumny.droxid '. Ti ^g emulsion layer made. To make the Aui-

Hydroxyethyl cellulose c. Compounds 1,

Made up to 11 i _V and V used with water. Compound V was in

After separating the image-receiving sheet from the contact with the green-sensitive silver halide test specimens was practically 15 emulsion layer in the treated test specimen, the compound IV in contact with no image dye recognizable. After 2 to 5 seconds of the red-sensitive silver halide emulsion layer announce prolonged exposure to air and the compound I was in contact with the blue sensitivity Reflection density of the transferred dye borrowed silver halide emulsion layer brought. the of the treated test specimen of 2.40 for a compounds I, IV and V can be in the corresponding -30 - Seconds - transmission determined. The corresponding silver halide emulsion layers are incorporated the density that would be obtained using the untreated one on the exposure side of the silver halo specimen was obtained, lay after a 5 minutes genide emulsion layers or continuous transfer time at 1.80, as can be seen from under the emulsion layers with respect to the expo curve C of FIG. 3 results. nation side. The first two arrangements will be

The test specimens with the silver halide emulsion are preferred. An assistant developer association and

layer were exposed through a stepped component, preferably a reducing agent such as

and for 60 seconds in contact with the described l-phenyl-3-pyrazolidone was in the recording

nen image receiving material with the described dematerial in contact with the corresponding

developing fluid. incorporated dye developer compounds

Immediately after the image receiving sheet of 3 ° tet.

had been separated from the recording material, the image-receiving layer contained a dye stain

was no dye in the image receiving layer of the medium, preferably an onium compound. Ge

Image receiving element visible. After a 2 to suitable onium mordants, coacervates are out

Exposure to air for 5 seconds resulted in N - η - hexadecyl - N - morpholinium ethosulfate and

however, in the image receiving layer of the image receiving 35 methyl - tri - η - dodecylammonium - ρ - toluenesulfonate,

element a thick layer of dye is visible. also the pickling agent N-n-octadecyltributylammo-

By incorporating a reducing agent, namely nium bromide and the like.

borrowed l-phenyl-3-pyrazolidone into the recording excellent three-color transference

material together with the offset indophenol images when developing with an alkaline

Dye developer connection takes place quite openly- 4 ° winding liquid is obtained, with the image dyes

lent no light absorption due to the offset staining - remained stable even when the pH was about 7

Substance developer compound. Furthermore it was completely reduced

obviously a faster transfer of color _. . . .

substance reached into the image receiving layer. example

The untreated test specimens were produced with a 45 die according to Production Example 2, ver developing liquid with 5 g of ascorbic acid per liter of dye forming a blue-green dye (Reducing agent) developed, so were also-developing compound was in the form of a gelatin case found fast transmission times. layer applied to a layer support. Upon contact with an alkaline developing liquid one

Example 6 5 ° pH of 14 and an image receiving element

with an image receiving layer with a quaternary

This example shows that the described mordant was found to produce a blue-green image-receiving layer

used indophenol dye developing compounds. The image-receiving layer remained blue-green,

Excellent for making r.; more multilayered - when the pH value has been adjusted to about 7.

For this purpose 2 sheets of drawings

Claims (15)

Patent claims: 1. A photographic material for color diffusion transfer process, consisting of of a support, at least one light-sensitive silver halide emulsion layer. at least one diffusible, colorless or pale colored, image dye-providing silver halide ent Winder connection, the absorption of which can be changed after exposure Silver halide emulsion layer or a layer adjacent thereto and, if appropriate, further ones Layers, characterized in that the developer compound is a compound of the following formula: D - (insulating link) - (SlD) in which D denotes an aromatic radical with a silver halide developer function, SID denotes an indophenol Dye residue, and in which the insulating link is the resonance system of the connection interrupting atomic grouping is. 2. Recording material according to claim 1, characterized in that there is at least one Contains developer compound of the following formula: D- (insulating link) - (Kupp) = N-Ar-OH in which D denotes an aromatic radical with a silver halide developer function, Kupp denotes an Color coupler radical which is bonded to the nitrogen atom in its coupling position, Ar an Arylene radical with 6 to 20 carbon atoms, in which the hydroxyl group is preferably in the p-position to the Nitrogen atom is located, and in which the insulating link is a the resonance system of the compound interrupting atomic grouping is. 3. Recording material according to claim 1, characterized in that there is at least one Contains developer compound of the specified formulas, in which D is an aromatic radical with at least two substituents consisting of hydroxy, primary amino or alkylamino radicals, is. 4. Recording material according to claim 1, characterized in that there is at least one Contains developer compound of the specified formulas, in which D is a hydroquinone radical. 5. Recording material according to claim 1, characterized in that it comprises: a) a blue sensitive silver halide emulsion layer and a yellow dye supplying indophenol developer compound, b) a green-sensitive silver halide emulsion layer and one a purple-red dye supplying indophenol developing agent as well as c) a red sensitive silver halide emulsion layer and one a cyan dye supplying indophenol developer compound, with the proviso that the indophenol developing agents in the emulsion layers or in adjacent layers are included. 6. Recording material according to claim 2, characterized in that there is at least one Contains 60 developer compound of the formula given, in which the color coupler residue (Kupp) is a Pyrazolone, Pyrazolotriazole or open-chain ketomethylene dye coupler residue or
the remainder of a phenol type color coupler. 7. Recording material according to claim 1, characterized in that there is at least one Layer containing an onium salt in water-permeable contact with the developer compound. 8. A photographic recording unit for color diffusion transfer process, consisting of the end a) a light-sensitive recording part, b) an image receiving layer and c) at least one container with an alkaline developing liquid that can be split open by the action of pressure for the recording material, characterized in that the photosensitive recording part is made of a recording material according to claim 1 exists. 9. Recording unit according to claim 8, characterized in that the image receiving layer between the support and the light-sensitive silver halide emulsion layer (s) of the recording material is arranged. 10. Recording unit according to claim 8, characterized in that the image receiving layer is arranged on a special support, in such a way that the image-receiving layer after Exposure of the photosensitive recording member can be applied to this. 11. Recording unit according to claim 9, characterized in that between the image receiving layer and an opaque or light-impermeable layer is arranged on the photosensitive layers is. 12. Recording unit according to claims 8 and 9, characterized in that the collapsible Container is arranged such that when pressure is applied, its contents between the image receiving layer and the furthest from the support of the photosensitive recording member Layer capable of pouring. 13. A photographic recording unit for color diffusion transfer process, consisting of a) a light-sensitive recording part, b) an image receiving layer, c) at least one container with alkaline developing liquid which can be split open by the action of pressure for the recording material and d) a terminating part connected to the recording part, characterized in that the photosensitive recording part is made of a recording material according to claim 1 exists. 14. Recording unit according to claim 13, characterized gekennzeicnnet that the rupturable container is arranged to hold its contents when pressure is applied between those of the substrate of the photosensitive recording part The furthest layer and the end part is poured. 15. Recording material or recording unit according to Claims 1 to 3, characterized in that that it contains at least one developer compound of one of the following formulas: OH