DE1101954B - Color diffusion transfer photographic process and related photographic material - Google Patents

Description

Color diffusion transfer photographic process and related Photographic material The invention relates to a color diffusion transfer photographic process, in which at least one light-sensitive image is used to generate at least one color image Material containing halogen silver emulsion layer is exposed, developed and with a receiving layer is brought into contact, as well as material for implementation such a procedure.

It has long been known in black and white photography to produce of direct positive images to one exposed halogen silver emulsion layer To develop a silver image and the halogen silver, which remains undeveloped, in an image-correct manner to be transferred to a receiving layer, where there is e.g. B. by a precipitant in a positive image is transferred.-This so-called silver salt diffusion process or halogen silver diffusion processes are also experimentally in the field of Color photograph rendered.

There are also already methods of producing a color photographic one Known direct positive image, in which one can manage without diffusing halogen silver. All previously known color photographic diffusion transfer processes however, require either an overly complicated material, or they are themselves extremely cumbersome or hardly affordable from a cost point of view.

The object of the invention is now to develop a simplified one and cheaper procedure, especially one in which on the basis of a A larger number of color reproductions are available in a single shot with the creation of a suitable photographic material.

The object is achieved according to the invention by that such a material is exposed and treated with an alkaline solution, that, closely related to halogen silver, d. H. in or adjacent to each emulsion, a developer substance and a diffusion-resistant coupler substance containing either in the coupling position by a pre-formed dye or a coupler part and in at least one non-coupling position by a diffusion-proofing position Group or in a coupling position by a diffusion-proofing group and substituted in at least one non-coupling position by a solubilizing group is, and that at least a portion of the diffusible image dye that is in the treatment with the alkaline solution in the exposed parts of the emulsions has formed if it is the developer substance associated with the halogen silver a color developer substance optionally containing solubilizing groups or if the developer is a black and white developer acts by transferring the halogen silver remaining after the alkaline treatment in developable state and developing by means of an optionally solubilizing agent Color developing agent containing groups generated on an image-receiving layer is transferred; or that a corresponding material, its diffusion-resistant coupler substance has any structure, is treated in the same way, but with the color developing agent that comes with. the halogen silver is connected or the to Development of the remaining halogen silver made developable is used, must contain at least one solubilizing group.

According to the invention, this method can be carried out with advantage a material can be used, which is on a support at least one light-sensitive Halogen silver emulsion layer and, if appropriate, customary intermediate and / or protective layers and developer and at least one of the coupler substances defined above contains, with a primary aromatic color developing agent Amino compound, is used. That I. the invention in particular with methods of manufacture concerned with multicolor images is preferably used to carry out the method Material with three differently sensitized halogen silver emulsions.-Means of this Process is achieved that from coupler substances due to their structure are diffusion-resistant, and from the oxidation products formed during development the developer substances used, a diffusible image dye is generated.

The developer substances contained in the material according to the invention include all types of silver halide developing substances, their types being dependent on the the specific use of the photosensitive material. But always will the developer substances corresponding to the halogen silver and the diffusion-resistant Couplers chosen. According to one embodiment of the invention, for. B. the developer substances, contained in the emulsion layer, from non-coupling developer substances, such as hydroquinone or certain stable derivatives thereof, or of essentially one diffusion-resistant developer, such as 4-phenyl-catechol or the like, their oxidation products, which arise in the course of the development of the halogen silver image, do not concern themselves with the diffusion-resistant coupler substance with the formation of a diffusible dye can implement. In other cases, described in detail below, can a developing substance of the mentioned non-coupling type in the sensitive layer together, but not necessarily in close contact with one of the color developing agents of the p-phenylenediamine type are present, which one with the diffusion-resistant couplers Form diffusible dye. In a reverse process in which both Types of developing agents in the photosensitive material must be either the color developing agent from the black and white developing agent during be isolated from the negative development, for example by using suitable Separating layers of selected permeability, or the negative development must with one suitable developer and carried out under such conditions that the color developer does not react too early with the coupler. By using suitable separating layers or corresponding means, it is also possible, exclusively a color developing agent, e.g. B. of the p-phenylenediamine type, in the photosensitive Material to be used together with the diffusion-proof couplers, in which case these Color developer substance both for negative development and subsequently as a color developer serves for the formation of the diffusible color image. In this case, the diffusion-resistant Coupler from the part of the emulsion in which the negative development takes place, so be isolated for a long time until the onset of color development of the remaining Emulsion and the formation of the diffusing positive image are desirable. In one Negative process, in which only a color developer substance in the photosensitive Material together with the non-diffusible coupler for the formation of diffusible If color images are present, the material can be exposed, activated with alkali and developed in contact with an image receiving layer, so that a negative color image of the subject overdiffused instead of a positive color image. Preferred Developing substances contained in the photosensitive material along with the diffusion-resistant Couplers are available for developing a negative image using the reversal process are among other things such known developer substances, their oxidation products do not form dyes with the diffusion-resistant couplers, e.g. B. black and white developing agents such as Hydroquinone, monomethyl p-aminophenol sulfate and 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and 4,4-dialkyl-3-pyrazolidones (U.S. Patents 2,688,549 and 2,751,300). Even Derivatives of these developer substances, e.g. B. the sulfur dioxide complexes described below, are effective in the light-sensitive material. As mentioned above, a Color developer of the p-phenyldiamine type for negative development using Reversal procedures can be used provided the coupler is in place the negative development is isolated.

The compound in the photosensitive material rides the diffusion-proof Couplers used or after a black and white negative development Color developing agents allowed to act include p-phenylenediamines, e.g. B. N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, N-ethylmethane-sulfonamidoethyl-3-methyl-4-aminoaniline and other N, N-dialkyl-p-phenylenediamine developing agents, as described in the Journal of the American Chemical Society, Vol. 73, pp. 3100 to 3125 (1951), as well as derivatives and complexes derived therefrom, such as the sulfur dioxide complexes and Schiff base derivatives as described below.

According to a first preferred embodiment of the method according to As mentioned, the invention uses a material which, in addition to a developing agent contains a diffusion-resistant coupler, which is in the coupling position by a pre-formed Dye or a coupler part and in at least one non-coupling position is substituted by a diffusion-proofing group. The in connection with The color developing agent used in such a coupler can, but does not have to be, solubilizing agents Groups included. - When reacting such a coupler with oxidized color developer substance becomes the dye-forming agent bound to the coupling position of the coupler substance through this Part of the molecule displaced. The adduct of the oxidized color developer with the after displacement of the dye-forming part of the molecule remaining coupler radical is, if the color developing agent used does not contain a solubilizing group, diffusion-resistant and therefore remains in the original layer; contains the If the color developing agent used has a solubilizing group, then the adduct be diffusible; therefore, at least when this adduct is colored, in the embodiment in question, such color developing agents are preferred, which do not contain any solubilizing groups. The one caused by the oxidized color developing agent Dye-forming compounds displaced from the coupling position of the diffusion-resistant coupler Part of the molecule is diffusible and represents if it is a finished dye acts, is itself the image dye or settles if it is a coupler part acts, with another molecule of oxidized color developer substance to the diffusible one Image dye around.

As is well known, the “coupling position” of the coupler molecule is understood to mean in the case of 5-pyrazolone compounds the carbon atom in position 4, in the case of phenols and a-naphthols also the carbon atom in the 4-position and in the case of open-chain couplers with reactive methylene groups, the carbon atom the methylene group in the atomic sequence-CO-CH2-CO-. Under "non-coupling positions" one understands the other positions of the respective connections.

As solubilizing groups that make the dyes diffusible in the process solutions mentioned, z. B. serve the following: -SO3H, -CH20H, -C2H40H, The diffusion resistance of the couplers can be determined by the molecular size or by the content of diffusion-proofing groups. The nature of such diffusion-making groups on the couplers is not particularly critical as long as only the couplers are given diffusion resistance and as long as the diffusion-making groups are not of a chemical nature which prevents the formation of the diffusible dyes by reaction with the oxidized color developing agent. Typical diffusion-proofing groups, as exemplified below for various specific couplers, are e.g. B. long-chain alkyl radicals bonded directly or indirectly to the coupler molecule; also aromatic residues of the benzene and naphthalene series, etc.

In the embodiment in question, a compound of the general formula Fl) -Y-Cp-DR is preferably used as the diffusion-proof coupler, in which R is a diffusion-proofing group bonded to a non-coupling position of the coupler part Cp by a stable bond D, preferably an aromatic group, and Fb denotes a dye part which is preferably diffusible through a content of at least one solubilizing group and which is attached to the coupler part Cp by a cleavable formation Y, e.g. B. -Hg-, -N = N-, -0-, -CH- or = CH-, -5-, -SS- or is bonded, where Z represents the atoms necessary to complete a ring.

These coupler substances are referred to below under the name "Class A coupler" described in more detail.

Instead of providing a special diffusion-proofing group their function can also be through the preformed dye or coupler part be fulfilled, namely when this is able, the entire molecule of the coupler to make diffusion-resistant, but if it is diffusible in split-off form itself is.

The non-diffusible coupler can also contain solubilizing groups, e.g. B. at least one in alkaline medium solubilizing group contain the one or the other or both parts created when the coupler splits into makes photographic developer solutions soluble. Usually it will be the solubilizing agent Group only attached to that part of the diffusion-resistant coupler, the one Forms part of the resulting diffusible dye, so z. B. in the case of class A couplers to the preformed dye-forming part. In certain circumstances it is desirable, after the completion of the transfer, to have other components than to wash out the diffusible dye. This can be made possible by having the part in question also with solubilizing groups, such as carboxyl or Oxyalkyl groups. The solubilizing groups are to advantage non-cleavable bonds attached to the coupler. If you have a bis-coupler or a coupler containing two dye-forming groups can also be used a solubilizing group on the one dye-forming group and a diffusion-proofing group Attach group to the other dye-forming group, making both parts at Cleavage of the bonds results in dyes, one of which is diffusion-proof and on Remains in place and the other is diffusible and into the image receiving layer wanders.

According to a second preferred embodiment of the invention contains the material used, in addition to the developer substance, a diffusion-proof coupler, in the coupling position by a diffusion-proofing group and in at least a non-coupling position is substituted by a solubilizing group. Color developing agents, the solubilizing groups, are also used in connection therewith may or may not contain. When reacting such couplers with oxidized Color developing agents are thereby attached to the coupling position of the coupler Bound diffusion-proofing group displaced as a diffusion-proof component it remains in the relevant shift and is no longer available for further proceedings significant; the adduct of the oxidized color developer substance with that after displacement of the diffusion-proofing group remaining coupler radical is now, since the diffusion-making group no longer, but the solubilizing group is contained therein, diffusible and represents the image dye.

In the embodiment in question, a compound of the general formula RY - Cp-DR 'is preferably used as the diffusion-resistant coupler substance, in which R' denotes an alkali-solubilizing group bonded to a non-coupling position of the coupler part Cp by a stable bond D and R denotes a diffusion-proofing group which by a cleavable bond Y, in particular an azo group or z. B. one of the groups -Hg-, -0-, -CH- or = CH-, -S-, -SS- or is bound to the coupler part, where Z has the meaning given above. These couplers are further described below under the heading "Class B Couplers".

Further examples of couplers of the embodiment in question are z. B. phenolic couplers containing a diffusion-proofing group such as -O C12 H25, contained in the 4-position, which is split off during color development, wherein a soluble one of the phenolic radical and the color developer molecule part Dye is formed; also phenolic couplers with the substituent -Hg O C O C H3, which is split off during color development; furthermore connections, by joining two reactive methylene couplers by means of a disulfide (- S-S -) group come about which compounds at the disulfide bond with the formation of two Molecules of soluble dye are broken down, each one of which is one of the original Coupler parts and contains the color developer part; also phenolic couplers, the are substituted in the 4-position with the group -S-C sHs-NO2, which are with oxidized Color developer with elimination of the nitrophenylthio group to a soluble coupled one Convert dye; also styryl dyes, such as 5-pyrazolones with the = C H-C6 H5 -Group in the coupling 4-position, which group under the color development Destruction of the color of the styryl dye and formation of a diffusing azomethine dye is split off, which contains the 4-pyrazolyl radical and the color developer part: also phenolic couplers which are in the 4-position with a diffusion-proofing group, such as alloxan or triketohydrind, which are substituted during color development is split off; Finally, alkylene-bis-pyrazolone couplers in which two are the same or various 5-pyrazolone couplers via the 4-position through an optional substituted methylene group, e.g. B. = C H-C6 H4-0 C18 H37, which Coupler during color development with the formation of two azomethine dye molecules are split, each of which is the color developing part and one of the 4-pyrazolyl groups contains, one or both of the dye molecules being soluble and transferable.

Couplers as used in the two embodiments discussed above have in common that they are used during the color development of the exposed emulsion layers in which they are located and while the emulsion layer get in contact with a z. B. is pickled receiving layer, with oxidized Color developing agents react, whereby the bond at the coupling position is broken and two products are made: The first product is a coupler and one Dye containing color developer molecule parts, and when this dye is a contains solubilizing group, then it migrates into the receiving layer in accordance with the image; the second product formed upon color development is inert except it contains the pre-formed dye group to which a solubilizing group is attached is bound, in which case this second product is a dye that is imagewise appropriate migrates into the receiving layer. In the latter case, it is the one containing the coupler part first product a diffusion-resistant dye that is used during the transfer process remains in the emulsion layer. As an alternative to this, the two products formed from a given coupler, both diffusible dyes be, d. that is, the first product, namely that by reaction between the coupler part The dye formed and the color developing agent is a diffusible dye because of the presence of a solubilizing group in the coupler part or in the color developer part or in both, and the second product, namely that of the coupling position split off can also be a diffusible dye.

The couplers as used in the two embodiments discussed above can be summarized under the following general formula: R-Cp-R 'wherein Cp is a coupler radical which is linked to a p-phenylenediamine or others Color developer substances form a dye, R a removable substituent in the coupling position, e.g. B. a diffusion-proofing group, the coupler makes diffusion-resistant in colloid layers, or a detachable pre-formed dye group, and R 'is a diffusion-imparting or a solubilizing group in non-coupling agents Means position of the coupler molecule.

According to a third preferred embodiment, a corresponding one is used Material, the diffusion-proof coupler of which has any structure, in connection with a color developing agent containing at least one solubilizing group. In a particularly simple case belonging here, an emulsion layer is used used, which have a latent silver halide image, a naphthol developer and as non-diffusing dye intermediate a coupler such as α-naphthylamine contains. As a developer z. B. be used a 1,2-dioxynaphthyline which is substituted in position 4 with a sulfonic acid or carboxylic acid group, so that during development the developing substance is oxidized and with the aromatic Amine couples to a diffusible ß-oxyquinonimide dye, which is image-correct can be transferred to a pickled receiving layer. Or it can e.g. B: in one or several emulsions of a photographic film as coupler 1-oxy-2- [d (2 ', 4-ditert. amylphenoxy) -n-butyl] -naphthamide can be used. When developing one Films with developers such as 4-amino-N-ethyl-3-methyl-N- (ß-sulfoethyl) aniline or other, similar developers listed below will be distributed according to the picture a soluble dye is formed, which becomes image-correct through duffusion and imbition can be transferred to the receiving layer. Of course, such can be solubilized Developers can also be used with couplers that contain a solubilized coupler unit, z. B. a sulfonaphthyl or sulfopyrazole unit. The presence of solubilizing However, groups in the coupler molecule are not required.

Couplers are preferred in the present embodiment of the general formulas Cp-D-R 'in which D is a stable bond which the diffusion-making group or groups R 'to a non-coupling position of the Coupler part binds Cp, and uses Cp-Y-R, in which Y means a cleavable bond, the a diffusion-proofing group R to a coupling position of the coupler part Cp binds.

These couplers are referred to below as "Couplers of Class C «described in more detail.

In the following the invention is illustrated by means of examples and the drawing described in detail. In the drawing, Fig. 1 shows schematically the generation a colored copy by exposure and development of material according to the invention and by diffusion transfer of the resulting color image onto a receiving layer, 2 shows a cross section through multilayer material according to. the invention.

As shown in step 1 of Fig. 1, the material consists of one Support 10, for example made of paper, which has a halogen silver emulsion layer 11 which carries a silver halide developing substance of the type specified and the coupler A of the class described above and the structure shown in the drawing. As can be seen from the structural formula of the coupler, it contains in the non-coupling 2-position of the phenolic group an alkali-solubilizing group and in the coupling 4-position of the phenolischeg group is an aromatic azo group which forms the Makes coupler diffusion-proof.

After exposure of the emulsion layer in part 12, as shown in the drawing, the material can be treated with an alkaline solution (alkaline activation) in order to initiate development and thus to achieve a silver image in part 12. The material can then be reverse exposed or otherwise made developable and then color developed. As development progresses, the coupler in the reverse exposed part 13 reacts with the oxidized color developing agent with cleavage at the azo bond, in which case a diffusible indoaniline cyan dye (B) is formed in parts 13 of the emulsion layer, as shown in Stufet , where the symbol R in the formula denotes the aromatic radical of the color developing agent used in the special case Image receiving material is in contact. As a result, at the same time as the reverse exposure material of step 1 is immersed in the color developing solution, the image receiving layer is also moistened with the color developing solution, and the two materials are then pressed together with the result that in the course of development and formation of the soluble indoaniline dye (B. ) in part 12 of this image-correct in, the image-receiving layer migrates and is inbibed and pickled to form the positive color reproduction shown in step 3, wherein a layer 20 shows the support of the image-receiving material, which is a colloid layer 21, z. B. made of gelatin, which contains a mordant and in part 22 the color image, which consists of the pickled dye (B).

Similarly, the procedure is performed if by a colored recording object full color reproductions can be made. The material stage 1 is then replaced by a photographic multi-layer film, of the three differently sensitized halogen silver emulsion layers arranged one above the other contains, e.g. B. corresponding to the main parts of the visible spectrum, and their each one a halogen silver evolution substance and one; the named couplers, contains. For example, the emulsions of the following examples are suitable for this purpose.

A multilayer material advantageously used according to the invention is shown in Fig. 2 in cross section in a greatly enlarged representation. In it means . a layer 30 a support, e.g. B. made of paper or a cellulose ester; one Layer 31 is an emulsion sensitive to blue light that has a yellowing effect Contains coupler, d. H. a coupler that allows you to transfer the image properly an image receiving layer provides a suitable diffusing yellow dye; a layer 32 means a red-sensitive reflection for the formation of diffusible blue-green images and a layer 33 of a green sensitive emulsion for forming diffusible magenta images. In addition, each emulsion layer contains a suitable developer substance, or one such is connected to it, for example in a: separate layer. layers 34 and 35 are intermediate layers, and a layer 36 is a protective layer. Of the Film is z. B. by a negative or positive color slide of an original or exposed through color partial images of it and then the action of an alkaline solution for developing silver images in the emulsion layers at the points of exposure subject. This is followed by color development in contact with an image receiving layer so that diffusing color images are in register from each emulsion layer in the image receiving layer migrate and form a full color reproduction of the original, as described in detail in Example 2 below.

The method thus comprises the color development of at least one emulsion layer, a latent positive image or an image-appropriate distribution of developable Contains halogen silver, the emulsion being either reverse exposed during color development or can be chemically obscured, in the presence of the non-diffusing couplers, for the formation of diffusing color images and their transfer to image receiving layers.

The following are characteristic examples of non-diffusing couplers according to the invention which form diffusible dyes with the oxidation products of color developers: Class A couplers Non-diffusible couplers of the phenol type or of the cyclic or open-chain reactive methylene compound type, which are substituted in the coupling position by pre-formed color molecules or parts are. For example the following: Examples of couplers containing such groups are as follows: 1-Oxy-4- {3- [4- (N-ethyl-N- (3-sulfoethylamino) -2-methylphenylazo] -pheny lazo @ -N- [8- ( 2,4-di-tert-amylphenoxy) butyl] -2-naphthamide 1-Oxy-4- {4- [4- (1-sulfophenyl -3 -methylpyrazolon- (5) -yl) -azo] -3-sulfophenylazo} -N- [ö- (2,4-ditert. Amylphenoxy) -butyl] -2-naphthamide disodium salt 1-Oxy-4- {4- [4- (1-p-sulfophenyl-3-methylpyrazolon- (5) -yl) -azo] -3-sulfophenylazo @ -N- {4- [a- (2,4 -ditert.amyl-phenoxy) -butyramido] -phenäthyl} -2-naphthamide dipotassium salt 1-Oxy-4- {3- [4- (N-ethyl-N - (3-carboxyäthylamino) -2-methylphenylazo] -phenylazo @ -N- [d-2,4-di-tert. Amylphenoxy) -butyl] - 2-naphthamide (sodium salt) 1-Oxy-4- (2,4-dinitrophenylthio) -N - [d - (2,4-di-tert-amyl-phenoxy) -butyl] -2-naphthamide 1-Oxy-4- {4- {3-methyl-4- [3- (1,5-disulfonaphthyl) -azo) -l-pyrazolone- (5) -yl) -phenylazo} -N- {4- [ α- (2,4-di-tert-amyl-phenoxy) -butyramido] -phenethylj-2-naphthamide dipotassium salt 1-Oxy-4- [4- (3-methyl-4- [3- (1,5-dsulfonaphthyl) azo] -1-pyrazolone- (5) -yl @ -phenylazole-N- [δ- (3 pentadecylphenoxy) butyl] -2-naphthamide dipotassium salt 1- [4- (p-tert-Butyl-phenoxy) -pheny 1] -3- [α- (4-tert-butyl-phenoxy) -proprionamido] -4- [1- (2-brotn-4-methylamino -5-sulfo-9,10-anthraquinonylazo] -pyrazolone- (5) α- {3- [a- (2,4-Ditert.amy 1-phenoxy) -acetamido] -benzoyl) -a- {3- [4- (N -ethyl-N-β-sulfoethylamino) -2-methylphenylazo ] -phenylazo} -2-methoxy-acetanilide (sodium salt) 1-Oxy-4- {4- [4- (1-p-sulfophenyl-3-carboxy-pyrazolon- (5) -yl) -azo] -3-sulfophenylazole-N- {4.- [a- (2nd , 4-di-tert-amyl-phenoxy) -butyramido] -phenethyl @ -2-naphthamide Class B Couplers Non-diffusing couplers which contain a solubilizing substituent in a non-coupling position and which react with oxidized color developers to eliminate a substituent from the coupling position to form a diffusible dye.

1. Non-detectable couplers which have an alkali-soluble group in a non-coupling position and a substituent attached to an azo group contained in the coupling position, which makes the coupler resistant to diffusion, which Coupler with oxidized color developer with cleavage of the azo bond and formation of a soluble dye react with the color developer:.

1-Phenyl-3- (3-sulfobenzamido) -4- (n-octadecyloxyphenylazo) pyrazolone (5) sodium salt α-Benzoyl-α- (4-oxy-2-pentadecylphenylazo) -N- [4- (35-disulfobenzamido) 1-acetanilide dipotassium salt 1-phenyl-3- (3,5-distifobenzamido) -4- [4- (3-methyl-5-pentadecyl) -pyrazolylazo] = pyrazolone- (5) -dototassium salt- 1-Oxy-4- (4-n-octadecyloxyphenylazo) -N- (β-sulfoethyl -2-naphthofhamide potassium salt 2,5-bis (3,5-disulfobenzamido) -4- (4-octadecyloxyphenylazo) phenol, tetrapotassium salt a-Benzoyl-a- [4- (3-methyl-5-pentadecyl) -pyrazolylazo] -4- (3,5-disulfobenzamido) -acetanilide (dipotassium salt) 1-Oxy-4- (4-octadecyloxyphenylazo) -N- [(3- (3,5-disulfobenzamido) ethyl] -2-naphthamide = dipotassium salt 1-Oxy-4- (4-octadecyloxyphenylazo) -3'-carboxy-35 1-Oxy-4- (4-octadecyloxyphenylazo) -2-napihthoic acid 4'-oxy-2-naphthanilide 1- [4- (4-tert: butylphenoxy) phenyl] -3- (3,5-disulfobenzamido) -4- (4-octadecyloxyphenylazo) -pyrazolone- (5) (dipotassium salt) 5- (3,5-Disulfobenzamido) -4- (4-octadecyloxyphenylazo) -2-heptafluorobutyramido-phenol (dipotassium salt) 2- [3,5-Disulfobenzamido] -4- (4-oxy-2-pentadecylphenyiazo) -5-methylphenol dipotassium salt 2- (3,5-Disulfobenzamido) -5-methyl-4- (4-octadecyloxyphenylazo) phenol dipotassium salt 1-Phenyl-3- (3,5-disulfobenzamido) -4- (4-octadecyloxyphenylazo) -5-pyrazolone disodium salt As in the case of compounds XI and XIX, the following couplers also contain two coupler parts and accordingly form two dyes with oxidized color developers, one of which is non-diffusible and the other is diffusible. These couplers show high coupling activity and little tendency to fog the emulsion layers compared to other class B couplers.

1- (p-sulfophenyl) -3-carboxy-4- (4-oxy-2-pentadecylphenylphenyl) = 5-pyrazolone sodium salt α-Benzoyl-α- (4-oxy-2-pentadecylphenylazo) -4- (3-sulfobenzamido) acetanilide, sodium salt 1- (p-Sulfophenyl) -3-carboxymethyl-4- (4-oxy-2-pentacedylphenylazo) -5-pyrazolone monosodium salt 1- Phenyl-3 - (3,5-disulfobenzamido) -4- (4-oxy-2-pentadecylphenylazo) -5-pyrazolone dipotassium salt 2. Non-diffusing couplers such as the following which contain an alkali-soluble group in a non-coupling position and an ether or thioether substituent in a coupling position which makes the coupler diffusion-resistant, which substituent is split off during coupling with a color developer forming a soluble dye: -1-oxy-4-dodecyloxy-2-naphthoic acid -. " 1-oxy-3 ', 5'-dicarbomethoxy-4-dodecyloxy-2-naphthanilide (Hydrolyzes to acid when dispersed) 2- (3,5-dichlorosulfonylbenzamido) -5-methyl-4- (4-nitrophenylthio) phenol (Hydrolyzed when dispersed to the acid) 3. Non-diffusing coupler rides an alkali-soluble group in a non-coupling position and an organometallic substituent in the coupling position, which is split off during color development, forming a soluble dye which forms the parts of the coupler and of the color developer, e.g. B. the following: 1-Oxy = 4-acetoxymercuri-2-naphthoic acid 4. Non-diffusing bis-coupler with two coupler molecules which are linked in the coupling position of both by an alkylidene or arylidene group, wherein at least one of the coupling molecules contains an alkali-soluble group in the non-coupling position, which bis-coupler in the coupling position during the Color development are cleaved, forming a diffusible dye with the color developer, e.g. B.

4,4'- (p-Octadecyloxyphenylmethylene) -bis- [1-phenyl-3 - (3,5-disulfobenzamido) -5-pyrazolone] -tetrapotassium salt 5. Non-diffusible couplers with an alkali-soluble group in a non-coupling position and a substituent derived from a geminal diol, such as alloxane, in the coupling position, which makes coupler diffusion-proof (USA, patent 2 632 702), which Substituent is cleaved during color development to form a soluble dye containing the parts of the coupler and the developer ;. z. B. 2- (3,5-Disuifobenzamido) -4- [5- (1-hexadecyl--3-phenyl-5-oxy-2,4,6-trioxohexahydropyrimidyl =)] -5-methyl-phenol dipotassium salt. 4,4 '- (2-Hexadecyl-diketohydrinden) -bis- [2- (3,5-disulfobenzamido)] -phenol-tetrapotassium salt When the above couplers are incorporated in halide silver emulsions and then developed in contact with a pickled receiving layer using alkaline color developing solutions containing 4-amino-N-ethyl-N- (β-oxyethyl) aniline as developer, color images are formed of the following colors obtained from corresponding couplers on the receiving layer: - Coupler I ...................... yellow II ...................... yellow III ....................... yellow IV .............. ..._..... f Orange yellow V ....................... yellow VI ....................... yellow VII ...................... yellow VIII ................... ... purple IX .. ................. blue-green X ...................... blue-green XI ..................... w- yellow. XII ...................... purple XIII ...................... yellow XIV ........................ blue-green XV ........... ........ blue-green XVI ...................... blue-green XVII ...................... purple XVIII ................: ....... blue-green Coupler XIX ...................... blue-green = a ...................... blue-green XIXb. . . . . . . . . . . . . . . . . . . . . . purple XX: ........: ............ Purple XXI ...................... yellow XXII ................: ..: .. purple XXIII ...................... purple XXIV ...................... blue-green XXV ...................... blue-green '-XXVI ....................... blue-green XXVII ...................... blue-green XXVIII ...................... purple XXIX. ..:. . . . ..:. ... = blue-green - .. XXX .-: ... ..... ........-. Blue green If the non-diffusing 'couplers of' classes A and B are used in the process according to the invention, they are given diffusible dyes with known p-phenylenediamine developers, e.g. B. with NN-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, - N-ethyl-ß-methanesulfonamidoethyl-3-methyl-4-aminoaniline, and other N, N-dialkyl-p-phenyleudiamine developers as described by B en t et al in the Journal of the American Chemical Society, Vol. 73, pp. 3100 to 3125 (1951).

Class C Couplers These are non-diffusing couplers that are not contain strongly acidic substituents and require the use of a color developer, which provides the alkali-soluble function. These couplers react with the color developer with the formation of diffusible color images'- and; have the following general formula: Cp-Y = R as mentioned above. Specific examples are as follows:

1-Oxy-4-phenylazo-N = methyl-2-naphthanilide 1-oxy-4-dodecyloxy-2-naphthanilide a, ä -dithio-bis-a-benzoylacetanilide 1-phenyl-3-methyl-4-benzal-5-pyrazolone a, ä - (4-Mefihoxybenzal) -bis-a-benzoylaceta.nilid Di- [4- (1-phenyl-3-methylpyrazolon- (5) -yl)] sulfide Di - [4- (1-phenyl-3-methylpyrazolon- (5) -yl)] -disulftd 1-Oxy-2 ", 5'-dibutoxy-4- [4- (sulfomethyl) phenylazo] -2-naphthanilide This class of couplers also includes couplers of the formula Cp-DR 'mentioned above, e.g. B. the following 1-oxy-2- [& - (2 ', 4'-di dert.amyl-phenoxy) -n-butyl] -naphthamide (U.S. Patent 2474293), 1- [p- (p' -tert.Butylphenoxy) -phenyl] -3- [p-tert. butyl-phenoxy) -propionylamino] -5-pyrazolone USA.-Patent 2 369 489), N- (p-Benzoylacetaminobenzenesulfonyl) -N- (x-phenylpropyl) - (o) -, (m) - or (p) - toluidine LTSA Patent 2,298,443.

Other couplers mentioned in the patents just mentioned are together with developers containing solubilizing functions similar to "bra'achbar, as well as many other couplers that are usually associated with developers, such as 2-amino-5-diethylamino-toluene, Form non-diffusing dyes.

Characteristic color developers which contain the solubilizing functions and which are particularly useful in connection with the non-diffusing class C couplers are e.g. B. the following: 3-methyl-4-amino-N-ethyl-N- (ß-sulfoethyl) aniline 3-methoxy-4-amino-N-ethyl-N- (ß-sulfoethyl) aniline 4-Amino-N-ethyl-N - (, B-oxyäthyl) -aniliti - 4-Amino-N, N-di (ß-oxyethyl) aniline 3-oxymethyl-4-amino-N, N-diethyl aniline - - 4-Amino-N-methyl-N- (ß-carboxyethyl) aniline 3-methyl-4-arxai, ns = N, N = di- (β-bxyethyl) aniline e tam idb-4-wa - min- « o: -N; I # = dl'- (@ ß-" öxyäfhyl) -am in 3-Methyi-4-amino-N-ethyllyl-N- (2,3-dioxy propyl) aniline sulfate 3- (3-oxypropoxy) -4-amino-N, N-diethyl aniline The representation of the couplers listed above is explained in patent application E 16264 IV a / 57 b.

In the following some embodiments of material and method according to the invention are given: Example 1 'A film; which contains the coupler and developer substance closely linked to the silver of the emulsion layer is prepared as follows: An undercoated cellulose ester film support is coated with an emulsion which has been prepared as follows: To a red-sensitive chlorobromine overemulsion containing 1 gram atom of silver in the form of halide silver, add 192cm3 a solution prepared as indicated below a hydroquinone-sulfur dioxide complex, 6100 cm3 of a 2.5% aqueous solution of the coupling Lers XIX a and gelatine, mucochloric acid hardener, Sapöuin üttd waters in such a_Mezrge, that the dried coating per unit area of 0.093 m2 -69 mg silver, 90 mg of the developer complex: jxnd - Contains 210 mg gelatin.

The film produced in this way corresponds to stage 1 of the drawing, where layer 11 'is the emulsion layer Aarst-elit just described. After exposure through an object to be photographed, the film is immersed in an aqueous-alkaline activation solution consisting of 1: Z0 g of sodium carbonate and 1 g of ascorbic acid per liter at a value of 12.0. At the same time, an image-receiving material consisting of a film substrate is dipped in a gelatin layer containing cetyl-trimethylammonium bromide as a mordant. htet is x; , in-die .., following9: .Eptwickl.erlösung, en; _ Benzyl alcohol :. . . . . . . . . . .-.: .-. . . . . . . . . . . . 10 ml 4-Amino-N = ethyl-N- (ß-öxyäthyl-) aniline 10g Sodium carbonate, anhydrous 20g Ascorbic acid .; .......... :: ..., .... 0.2 g Water-- .........................: ... on 11. pg. . . . . . . ; __ -_ _:> __. . . . . . . . . 11.0 After 45 seconds, the film and the receiving layer are pressed against each other. This is followed by reverse exposure of the remaining halogen silver through the support of the film, with the result that the coupler in the reverse-exposed parts 13 of the emulsion forms a diffusible dye (B) with the color developer substance, as in Stage 2 of the drawing shown. The dye then migrates into the receiving layer in an image-correct manner. The film and the receiving layer are taken apart after 10 minutes, a color reproduction being obtained on the receiving layer which looks like stage 3, the dye on the parts 22 of the colloid layer 21 being stained.

Instead of the above-mentioned mordant, the receiving layer in the method according to the invention as a mordant z. B. also contain polymers of aminoguanidine derivatives of vinyl methyl ketone, which are described in US Pat. No. 2,882,156 and the structure exhibit. Other suitable mordants are e.g. B. the poly-2-vinyl-pyridine-metho-p-toluenesulfonate and similar compounds as well as cetyl-trimethylammonium bromide, etc. described in US Pat. No. 2,484,430 Case of a layer of polyamide or another polymer product. The above-mentioned metah-hydroquinone-sulfur Dioxyd complex is prepared as follows: Elon complex 172.2 g of monomethyl-p-aminophenol sulfate are added to a solution of 40 g of sodium hydroxide and 25 g of sodium sulfite in 500 cm3 of water. The free base is extracted in a separatory funnel using 200 cms of isopropyl alcohol. Sulfur dioxide is then passed into the solution until the white precipitate initially formed dissolves again to form a deep orange solution.

Cooling the solution in a dry ice-acetone bath gives a white crystalline product which is filtered and dried.

Hydroquinone complex -110 g of hydroquinone, dissolved in 700 cm3 of water at 40 ° C, are saturated with sulfur dioxide and cooled to 5 ° C. The yellow product which crystallizes out is filtered off and dried. Now one prepares the hydroquinone-sulfur Dioxide complex by dissolving 1 g of the above-mentioned Metol complex and 15 g of the hydroquinone complex in -50 cm3 of ethanol containing 10 cm3 of water.

The procedure of Example 1 can also be carried out in a similar manner by simply inserting the film directly into the after the initial image exposure Color developing solution is immersed and after 1 minute it with that of the color developing solution brings wetted receiving layer into contact. The negative development is allowed go, and during this time the black and white developing agent diffuses from the film and is replaced by the color developing agent. After the reverse exposure diffusible color images are formed in the emulsions in question and migrate image-correct in the receiving layer.

In the manner described in Example 1, other films, which contain class A, B and C couplers by the reverse method of generation of positive images can be used in an image receiving slide. If you are a matchmaker of class C, one must of course use the necessary solubilizing agents Use developing substances for the color developing solution.

Example 2 A multilayer material is prepared, the Coupler of the Classes A and B and a black and white developing agent closely associated with each emulsion contains, using a developer substance that is unable to with to form the couplers diffusible dyes.

For this purpose, it is carried on a film carrier provided with an underlayer the following layers on: base layer to a 1 gram atom of silver in the form of A red-sensitive silver chlorobromide emulsion containing halogen silver is added to 192 cm3 of a solution of the metol-hydroquinone-sulfur dioxide complex described above, 6100 cm3 of a 2.5% aqueous solution of coupler XIX a and gelatin, mucochloric acid hardener, Saponin and water in such an amount that when applying the mixture to about 162.5 cm2 film base the dried coating per unit area of 0.093 m2 62 mg Contains silver, 90 mg of the developer complex and 210 mg of gelatin.

Second layer A mixture of 4540 g of a 100 / own aqueous gelatin solution, 12 500 cms of a 10% aqueous solution of potassium n-octadecyl hydroquinone monosulfonate, also of saponin, mucochloric acid and water is applied to an area of about 465 m2 in a strength of 91 mg gelatine and 25 mg of the mentioned potassium salt per unit area of 0.093 m2 applied. The aforementioned hydroquinone compound in the form of the potassium salt in this and in the fourth layer, described below, serves as an antioxidant and helps to keep the development products in the right layers.

Third layer The layer is made in the same way as the base layer with the exception that a green-sensitive chlorobromide silver emulsion is used, which contains 1 gram atom of silver, and that the solution of the coupler XIX a by 5250 g of a 10% aqueous solution of coupler XIX b replaced and applied in such a way that that per unit area of 0.093 tn2 62 mg of silver, 30 mg of the coupler XIXb- and receives 95 mg of the developer complex.

Fourth layer - This layer is applied like the second layer with the exception that yellow silver according to C a r e y-L e a in an amount of 9.8 mg added per unit area of 0.093 m2.

Fifth layer This layer is made in the same way as the base layer applied with the exception that a blue-sensitive chlorobromosilver emulsion, the 1 gram atom of silver contains, and that one uses the coupler XIX a by 7850 g of a 2a / o strength aqueous solution of the coupler V-II replaced by the addition of 157 g of coupler VII, dissolved in 4500 cm3 water and 450 cm3 28% ammonia solution, to 2700 g of a 10% gelatin solution and neutralization of the solution with citric acid available to a pu of 6.5 and topping up with water to a total weight of 7850g- is. The finished layer contains 62 mg of silver per unit area of 0.093 m2, 90 mg of coupler VII, 9-5 mg developer complex and 210 mg gelatin. Sixth layer Saponin, mucochloric acid and water are added to -4540 g of a 10% gelatin solution in an amount suitable for applying one layer. enable that Contains 91 mg gelatine per unit area of 0.093 m2. This layer serves as a Protective layer over the other layers.-The film thus obtained is essentially the same that shown in Fig. 2, wherein with 30 the carrier, with 31, 32 and 33 the emulsion layers and at 34 and and 35 the intermediate layers and at 36 the outer protective gelatin layer are designated.

After exposure through a positive color slide or other object the film can be immersed in the activation solution described in Example 1. Similarly, the pickled image-receiving layer with the developing solution of Example 1, and after 45 seconds the film and image receiving layer compressed. This is followed by a reverse exposure of the remaining halogen silver through the support of the film with the result that the couplers in the reverse exposed Parts of the emulsions form diffusible dyes with the color developing agent. These dyes then migrate into the image-receiving layer in an image-correct manner. The film and the receiving layer are taken apart after 10 minutes, whereby one Preserves full color reproduction on the receiving layer. If you want more copies, you can do it by moistening the multilayer material and transferring parts of the dye images remaining therein are retained on new image-receiving layers.

In the above examples, the silver halide developing agent be incorporated into a colloid layer adjacent to each emulsion layer, rather than being incorporated into the emulsion layers themselves. The developer substances can also in the material in the form of any of those described in the following examples Complex salts and derivatives are present.

It is extremely surprising to get through. those described above Process gives full color reproductions when one considers that in the process the simultaneous, image-accurate transfer of the dyes to a single image-receiving layer without undue lateral diffusion is required, and if one is taken into consideration draws that the hitherto only practically usable color transfer process with sequential and non-simultaneous transfer of dyes work from colloid relief images.

The development methods according to the invention, in which non-diffusing Dye intermediates are used, is the formation of the oxidation product the developer substance and the formation of the diffusing dye image Result and - takes place under - the control of the reduction of the developable halogen silver positive image.

Example 3 As mentioned above, the various transmission methods, in which non-diffusing couplers the. Classes A, B and C are used also be performed when the process of forming the diffusing dye image required color developing agent is present in the material. In this case it is only necessary to adapt the material and the process accordingly, such that the negative development takes place before the color development, as in described below.

A halogen silver emulsion is produced by adding 150 cm3 of water and 200 cm3 of a 10% gelatin solution to 100 cm3 of a silver bromide emulsion adds, which contains 1 gram atom of silver and 64g of gelatin per 780g of emulsion. To 10 cm3 this diluted emulsion is added -a) 25 cm3 of one from 0.8 g of coupler XIXb, 40.0 cm3 of an aqueous gelatin solution, 8.0 cm3 of a 7.5% saponin solution and 40.0 cm3 cm3 of water existing solution; b) 10 cm3 of a 20% solution of the tetrasodium salt of ethylenediaminetetraacetic acid, c) 20 cm3 of an aqueous solution, consisting of 1000g of water, 40g of sulfur dioxide and 50g of a color developing agent Schiff's base derivative prepared as follows: Dissolve in 50 cm3 of water 0.05 moles of N, N-diethyl-3-methyl-4-aminoaniline. 0.06 moles of o-sulfobenzaldehyde are added to this (Sodium salt) in 100 cm3 of water. The mixture is stirred for 30 minutes, left overnight stand, the yellow crystalline Schiffsehe base is filtered off and crystallizes out Ethanol.

The emulsion provided with additives a), b) and c) is in a 0.15mm thick on an undercoated cellulose acetate film backing applied.

The emulsion is then exposed through a subject and treated 30 seconds with an 18% aqueous solution of titanium chloride (pH = 0.9) then against an image receiving material which was previously dissolved in an aqueous solution of 15 g of sodium carbonate and immersing 5 cc of benzyl alcohol in 300 cc of water (pH adjusted to 12.0). After one minute the emulsion and receiver separate, leaving a purple Positive image remains on the image receiving surface.

Apparently the acidic titanochloride solution evolves in this process the exposed emulsion in the presence of the color developer substance without dye formation. If the p $ of the emulsion by contact with the alkaline image-receiving layer is increased, so ceases the developer effect of the titanochloride, selectively to be, all of the leftover halogen silver becomes evolvable and reduced to silver. The resulting oxidation products then convert the color developer substance into its oxidized form, which couples with the coupler XIXb, the coupler substance is cleaved at the azo bond and a diffusing positive purple color image which migrates into the image receiving layer.

Example 4 A reverse color transfer process can also be carried out in this way be that both the developer substance for the negative development and the color developing agent is incorporated into the light-sensitive material will.

For this purpose one prepares a photosensitive material that a slowly developing fogged silver halide emulsion on a support; and about it has a rapidly developing emulsion, which in a limited amount Black and white developing agent, e.g. B. the Metol-hydroquinone-sulfur dioxide complex from Example 1, furthermore a coupler (e.g. the coupler XIXb) and a color developer substance, as described in Example 3 under c). After exposure of the material through a subject, it is mixed with an alkaline solution to develop a -negative silver image in the presence of the slowly reacting color developer substance treated. The remaining black and white developer migrates into the underlying Emulsion and is consumed to develop the fogged halogen silver. During the reverse exposure of the emulsion layer, the color developing agent develops a positive silver halide image, and the oxidation product of the color developing agent couples with coupler XIXb to form a positive purple color image which migrates into the pickled image-receiving layer, which one before or afterwards in contact with the emulsion layers. Example s The reverse dye transfer process according to the invention can also be carried out when the black and white developing agent for the negative development is contained in the photosensitive material and the color developer is supplied from the outside. B. a movie her, which has on a carrier one or more halosilver emulsions which one of the couplers of classes A, B and C discussed above, e.g. B. Coupler IX, and also contain a silver halide developing agent such as catechol. The film is exposed through a subject and the development through treatment started with an alkaline solution. Once the negative development is over is, the emulsion of the action of compounds of the borate type, e.g. B. Sodium metaborate, which interacts with developing substances such as catechol, implement while destroying their ability to develop. Shortly thereafter, the leftover will be Halide silver of the emulsion exposed or chemically fogged and exposed to the action a color developing agent for use with class A, B or class couplers C subjected to a suitable type while the emulsion is in contact with a pickled As a result, the color developing agent develops the remaining positive halosilver image, and the oxidation product of the color developing agent sets with the coupler with elimination of its arylazo substituents Formation of a diffusing dye, which is image-correct in the receiving layer wanders and a positive single or multi-colored reproduction of the original in question results.

To carry out this process, the borate or the like can be used Mordant placed on the surface of the receiving layer in contact with the emulsion and the color developer substance in an underlying layer, in in which case the developer substance, e.g. B. the catechol, and the coupler compound containing material exposed and then both the emulsion and the Receiving layer treated with the alkaline solution and pressed against each other with the result that the catechol completely develops the negative before the borate diffuses into the emulsion and makes the catechol ineffective. After this the remaining halogen silver has then been made developable, developed the color developing agent that has diffused into the emulsion, the positive halogen silver and forms with the coupler the diffusing dye which is in the image receiving layer wanders.

Alternatively, only the mordant and the color developer substance can be used be contained in the image receiving layer, and after the completion of negative development The remaining catechol can be removed from the emulsion by treating it with a borate solution can be made ineffective, whereupon the remaining halogen silver is exposed and color development in contact with the receiving layer for transferring a Dye image makes on this.

It is also possible to use the development suppressive compound, z. B. the metaborate, in an intermediate layer of the photosensitive material, which is isolated from the emulsion layer or layers by separating layers, which slowly moves the borate into the emulsion layer after the negative development has been completed let diffuse.

The image-receiving layer or material can be used as desired also contain only the mordant, in which case the borate, the color developer substance and alkali after negative development and reverse exposure from solution the photosensitive material can be allowed to act, which one then against the Receiving layer presses, whereupon a diffusing dye image is formed and applied the receiving layer is transmitted as described above.

It has been shown above that the developer substances are the photosensitive Material either as simple compounds by themselves or in the form of complex salts, z. B. with sulfur dioxide, can be incorporated. This second alternative is particularly advantageous because it is a light-sensitive material, halogen silver, coupler and contains developing substance complex, is more stable and over time as well little changes under unfavorable temperature and humidity conditions the sensitometric and other properties suffers. The following examples describe further methods for introducing the developer substances into the photosensitive Material.

Example 6 An amine-sulfur dioxide salt is prepared by addition one equivalent of sulfur dioxide to a solution of an oxyalkylamine, e.g. B. des 2-diethylaminoethanol, in water. 50.0 g of this liquid product are added 1.0 g of 4,4-dimethyl-1-phenyl-3-pyrazolidone and 10.0 g of hydrodhinone. The formed product can be used to form a silver halide emulsion, as described in Examples 1 and 2, add in an equivalent amount, after which the sensitive material is reversed develop and place the monochrome or multicolored images on a pickled receiving layer can transfer.

Example? An oxyalkylamine is used as described in Example 6, with sulfur dioxide and adds 50 g of the product obtained 11.0 g of 2-amino-5-diethylaminotoluene. An equivalent amount of this product can be an emulsion together with a coupler, as described in Example 3, c), incorporate and the material according to the reverse procedure given in Example 3 to develop.

Example 8 A metoquinone-sulfur dioxide complex is prepared, by adding 60g metoquinone to 100 cm3 of water at 50 ° C. Sulfur dioxide is passed through until all of the metoquinone has dissolved. When cooling to 5 ° C and further Introducing SO2, orange-yellow crystals form, which are filtered off and dried. A solution of an equivalent amount of the product in aqueous alcohol can be in the Examples 1 and 2 used instead of the Metol-hydroquinone complex and that Color transfer processes can be carried out in an analogous manner. -. Example 9 To 42 g of the color developer substance 2-amino-5-diethylaminotoluene in 100 g of water 12 g of gaseous sulfur dioxide are added. The developer substance goes into solution, the color of the solution changes from pink to straw yellow. An equivalent amount the solution can be used instead of the Schiff base derivative in Example 3, c) to introduce the developer into the emulsion, and the color transfer process is carried out in the same way.

According to Example 3, a Schiff base developer is used to prepare stable emulsions which contain color developer substances. Presumably the Schiff base mentioned there, the sulfobenzaldehyde derivative of the developer in question, has the following structure: These and other Schiff bases, which can be obtained by reacting primary aromatic amino compounds suitable as halogen silver developers with e.g. B. sulfonated hydroxylated - or carboxylated, aromatic aldehydes of the benzene or naphthalene series obtained can be used in emulsion layers or in layers adjacent thereto in processes according to the invention as developer substances. The compounds have the general formula RN-CH-R ', _ -. where R denotes a monocyclic aryl group of the benzene series which is substituted in ortho- or para-position by - OH, - N H2, - NHR "or - NR"2; R "denotes a hydrocarbon radical, in particular a short-chain alkyl group, especially a methyl or ethyl group, and R 'denotes an acidic aliphatic, cycloaliphatic or aromatic group, in particular from the benzene or naphthalene series, with solubilizing groups such as Carboxyd and Sulfo groups or water-soluble salts thereof, as well as oxyalkyl groups, for example an oxyethyl group, are substituted -Ethyl-N- (ß-oxyethyl-4- (o-sulfobenzylideneamino) aniline sodium salt, N, N-diethyl-4- (2,4-dioxybenzalamino -) -3-methylaniline, N-ethyl - 3 - methyl - N - (ß - methylsulfonamidoethyl) - 4- (2-sulfobenzalamino) aniline sodium salt.

It has also been shown that the sulfur dioxide complexes of the Schiffs Base developer (Example 3) give stable emulsions. These connections seem even more stable than the corresponding complexes of developer and des To be sulfur dioxide.

Slowly or essentially non-diffusing in colloidal layers Developing agents are used for photosensitive materials that have coupler compounds contains, extremely beneficial. This subheading includes E.g .: 2,5-dioxydiphenyl, 3,4-dioxydiphenyl, 2,3-Dioxydiphenyl, 4-phenoxypyrocatechol, 4- (2,4-di-tert.amyl) -phenoxypyrocatechol, 4- (2-cyclopentenyl) pyrocatechol, 1,2-diethoxalyl-4-phenoxypyrocatechol, 1,2-diethoxalylphenylpyrocatechol and 1,2,3-triethoxalyl pyrogallol.

These connections show little tendency during the color transfer processes according to the invention to migrate into the image receiving layer. If you wish, you can do this Developing substances converted into the corresponding complexes with sulfur dioxide and used in the photosensitive material.

As described, the developing substances of the p-phenylenediamine type settle in oxidized form in the process according to the invention with class A couplers, B and C to form diffusing dyes. While photosensitive Material containing developer and non-diffusing color former in the reversal process described is particularly useful, it is equally useful usable in negative-positive color transfer processes such as those described e.g. B. in the patent application E 16264 IV a / 57b. You can also use the procedures described there an emulsion that is a color developer. Federation . -a . _ Coupler - which contains AB or C, exposed and activated with @ lkäli, with the result that the formed oxidized developing agent with the coupler under Formation of a diffusing dye image that couples into an adjacent image receiving layer migrates and creates a negative color image there.

Photosensitive material according to the invention can be more similar Way to be developed in this way; that one can be negative or positive or negative and Obtains positive color images by transferring them from the same material. This means, an exposed emulsion containing color developer and couplers can be mixed with an alkaline solution activated and the diffusing negative color image formed transferred to a receiving layer as previously described; on it can-that Leftover halosilver can be exposed, so that it can deal with the leftover Color developer or freshly added developer diffuses positive color image; and this can be transferred to a second image-receiving layer as a positive color reproduction will.

The optimal amount of the material to be used for the photosensitive material Developer will vary depending on the embodiment of the process used, however amounts are on the order of 0.4 to 1.0 moles per mole of halosilver in general particularly suitable.

The light-sensitive layers of material, the developer and couplers for carrying out the method according to the invention together, can vary widely in their composition, but are included in the In the vast majority of cases, silver halide is emulsified in a suitable dispersion medium.

The photographic emulsions used in accordance with the invention are of the developable type. The emulsions can be chemically sensitized by any conventional method. They may have naturally active gelatin to the base, or it can be added to sulfur compounds, such as are described in the USA. Patents 1,574,944, 1,623 499 and 2,410,689.

The emulsions can also be mixed with salts of precious metals such as ruthenium, Rhodium, palladium, iridium and platinum. Characteristic connections are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, the to be used for sensitization in amounts below those that cause a noticeable have anti-haze effect, as described in US Pat. No. 2,448,060, or as an antifoggant in larger amounts, as in the U.S. patents 2,566,245 and 2,566,263.

The emulsions can also be chemically sensitized with gold salts as described in U.S. Patent 2,399,083, or stabilized with gold salts as described in U.S. Patents 2,597,856 and 2,597,915. Suitable Compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, gold trichloride and 2-aurosulfobenzothiazole methochloride.

The emulsions can also be chemically combined with reducing agents such as tin (II) salts (US Pat. No. 2,487,850), polyamines such as diethylenetriamine (US Pat. No. 2,518,698), spermine (US Pat. No. 2,521,925) or Bis - (ß-aminoethyl) sulfide and its water-soluble salts (US Pat. No. 2,521,926), be sensitized.

They can also be optically sensitized with cyanine and merocyanine dyes, as in U.S. Patents 18-16 301, 1 846 302, 1942 854, 1990 507, 2 112 140, 2 165 338, 2 493 747, 2 739 964, 2,493,748, 2,503,776, 2,519,001, 2,666,761, 2,734,900, 2,739,149 and in British Patent 450,958.

The emulsions can also contain mercury compounds (USA patents 2,728,663, 2,728,664 and 2,728,665), with triazoles (U.S. Patent 2,444,608), with azaindenes (U.S. patents 2444605, 2444606, 2444607, 2 444 609, 2 450, 397, 2 713 541, 2 743 181, 2 716 062, 2 735 769, 2 756 147, 2 772 164 and essay von B i r r in "Journal for Scientific Photography", vol. 47, p. 2, year 1952), with quaternary benzothiazolium compounds (U.S. Patent 2131038) or stabilized with zinc and cadmium salts (US Pat. No. 2,839,405).

The emulsions can also contain speed-increasing additives such as Compounds of the quaternary ammonium type (U.S. Patents 2,271,623, 2,288,226 and 2,334,864) and of the polyethylene glycol type (U.S. Patent No. 2,708,162).

The emulsions can contain suitable plasticizers for the gelatin, e.g. B. Glycerine. Furthermore, a dioxyalkane, such as 1,5-pentanediol; Ester of an ethylene bis-glycolic acid, such as ethylene bis (methyl glycolate), according to U.S. Patent 2,904,434; also bis (ethoxydiethylene glycol) succinate according to French patent specification 1 200 094; or a polymeric hydrosol made by Emulsion polymerization of a mixture of an acrylamide and an acrylic acid ester and a styrene type compound according to U.S. Patent 2,852 386. The plasticizer can optionally be added to the emulsion before or after used sensitizer can be added.

The emulsion can be hardened with a suitable gelatin hardening agent such as formaldehyde. Furthermore with a halogen-substituted aliphatic acid such as mucobromic acid ( USA. Patent 2080019); a compound having multiple acid anhydride groups such as 7,8-diphenylbicyclo- (2,2,2) -7-octene-2,3,4,5-tetracarboxylic acid dianhydride; or a dicarboxylic acid or disulfonic acid chloride such as terephthalyl chloride or naphthalene-1,5-disulfonyl chloride (U.S. Patents 2,725,294 and 2,725,295); a cyclic 1,2-diketone such as cyclopentane-1,2-dione (U.S. Patent 2,725,305); a diester of methanesulfonic acid such as 1,2-di (methanesulfonoxy) ethane (U.S. Patent 2,726,162); also 1,3-dioxymethyl-benzimidazol-2-one ( USA. Patent 2732316); a dialdehyde, the aldehyde groups of which are separated by 2 to 3 carbon atoms, or a sodium sulfite derivative thereof, such as β-methyl-glutaraldehyde-bis-sodium bisulfite (French patent specification 1,169,616); a bis-aziridine carboxamide, such as. B. trimethylene-bis- (1-aziridinecarboxamide); finally 2,3-dioxy-dioxane according to US Pat. No. 2,870,013.

The emulsions can contain a coating aid such as saponin; also a lauryl or oleyl monoether of polyethylene glycol (US Pat. No. 2,831,766); a salt of a sulfated or alkylated polyethylene glycol ether ( U.S. Patent 2719087); an acylated alkyl taurine, e.g. B. Oleylmethyltaurine (U.S. Patent 2739891); the reaction product of a dianhydride of tetracarboxybutane with an alcohol or an aliphatic amine having 8 to 18 carbon atoms which is treated with a base, e.g. The sodium salt of the monoester of tetracarboxybutane, as described in U.S. Patent 2,843,487; a water-soluble maleopimarate or a mixture thereof with a substituted glutamate (U.S. Patent 2,823,123); an alkali metal salt of a substituted amino acid, e.g. B. disodium N- (carbop-tert.octyl-phenoxy-pentaethoxy) -glutamate according to French patent specification 1205155; a sulfosuccinamate such as tetrasodium N- (1,2-dicarboxyethyl) -N-octadecyl sulfosuccinamate or N-lauryl disodium sulfosuccinamate.

The additives described can be used in various photographic types Emulsions can be used. Except in X-ray and other not optically sensitized You can also use emulsions in orthochromatic, panchromatic and ultra-red sensitive Emulsions can be used. You can use the emulsions before or after at most used sensitizers are added. As light sensitive salt various silver salts, such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide are used will.

To represent the halide silver dispersions for the halide silver emulsions can be used as a dispersant for the halogen silver in its representation gelatin or other colloidal material such as colloidal albumin, a cellulose derivative or a synthetic resin, e.g. B. a polyvinyl compound can be used. As colloids can further z. B. used: polyvinyl alcohol or hydrolyzed polyvinyl acetate (U.S. Patent 2,286,215); largely hydrolyzed cellulose ester, like to an acetyl content of 19 to 26% hydrolyzed cellulose acetate; water soluble Ethanolamine cellulose acetate (U.S. Patent 2,322,085); Polyacrylamide with a Acrylamide content of 30 to 60 ° / a and a specific viscosity of 0.25 to 1.5 or an imidated polyacrylamide with similar acrylamide content and viscosity (U.S. Patent 2,541,474); Zein (U.S. Patent 2,563,791); Polyvinyl alcohol containing cyanoacetyl groups such as that described in U.S. Patent 2,768,154 Copolymer of vinyl alcohol and the cyanoacetic acid ester of vinyl alcohol; a urethane carboxylic acid of the type described in U.S. Patent 2,808,331.

Compatible mixtures of two or more can be used as desired these colloids can be used to disperse the halogen silver. Also can Combinations of the mentioned antifoggants, sensitizers, hardeners etc. can be used.

From the above description it can be seen that the monochrome Working single-layer photosensitive material can be used, which is a the emulsions prepared according to Example 1 contains. One can also be useful Results obtained by putting in a single emulsion layer of a photosensitive Material is a mixture of one or more of the dye-transferring cyan, Incorporated purple or yellow couplers. Similarly, in the manner of the known Imbibition color copying process separate films, one of which each one blue-green, one purple and yellow coupler, exposed and in register with one another with an image receiving layer be developed to form a full color reproduction. Similarly, can three kinds of photosensitive material, one of which is for one of the primary colors of the visible spectrum is sensitive, filter exposed through a color slide and then in register and in contact with the image receiving layer for generation a positive color reproduction can be developed.

As shown in the examples above, the are non-diffusing Couplers and the developer compounds in separate emulsion layers are sensitive Material dispersed uniformly. If desired, the close association of emulsion, Developer substance and coupler take place in various forms, so it can be, for. B. be desirable for certain special purposes, the couplers, the developer substances and to incorporate the halide of silver in the form of packets, as in the U.S. Patent 2,698,794 is described, so that at least two differently sensitive silver halide emulsions and the corresponding couplers for subtractive color photography in a single one Layer are closely linked in the form of a mixed package system. According to one embodiment the coupler substance, the developer substance and the halogen silver in the Package intimately mixed; according to another embodiment, only the coupler substance and the emulsion is in the package, and the developing agent is in the package or contain the die surrounding the packages. Also other methods of incorporation the coupler and halogen silver in packets are useful. In a similar way can use the halide silver emulsions, for example those in the above examples 1 and 2 -described color developer and coupler substances, in separate layers present if this is for any reason towards the association in the same Emulsion layer is preferred.

In some cases it is also desirable to use other intermediate layers, z. B. to provide those that restrict diffusion in areas where the normal The functioning of the processes can be impaired.

It is obvious that besides others. z. B. known color development processes the uniform and convenient application in particular of the liquid mixtures used to initiate the development to the sensitive material containing the coupler and developer substances according to the invention, too. can be carried out with the aid of fragile containers or their functional equivalents, which: with the sensitive material of the receiving layer or another material. as described in U.S. Patents 2,698,244, 2,559,643, 2,647,049, 2,661,293, 2,698,798, and 2,774,668. The photosensitive material described above is useful in cameras in both sheet and roll form, in combination with containers containing solutions of e.g. B. contain alkali, color developing agents and the like and which are arranged so that after the object has been taken up in the photosensitive material, the contents of the container are set free as desired, in an amount suitable for the formation of diffusing color images, which are then transferred to receiving layers.

As mentioned above, the receiving layer is for receiving the diffusible Color images are not necessarily separated from the light-sensitive arrangement, but rather can be part of it. That said, it's just as useful and in some It is preferable in cases where the image-receiving layer is a component of the emulsion layer is and the coupler and developer substances in the emulsion or an adjacent one Colloid layer are present. A typical material of this type consists of about a carrier having a pickled colloid layer thereon and the emulsion or emulsions containing the coupler and the developing agent thereover. When using easily soluble emulsions, such as those based on polyvinyl alcohol or an alkali-soluble cellulose ether phthalate, or a wet or dry one strippable layer of such carriers between the emulsion and the image-receiving layer is arranged, the developed emulsion layer can then be removed from the receiving layer on which the color image remains. Similarly, the Receiving layer initially bonded to the outer emulsion surface, e.g. B. with Help of a peelable layer. In this case, it is beneficial through the wearer of the photosensitive material through it, except when the receiving layer itself is transparent. The non-diffusing couplers according to the invention can instead of may also be contained in one of these adjacent layers in the emulsion layer.

As stated above, the diffusing color images can be imagewise be transferred to the receiving layers, regardless of whether the layer in which the color image is formed is in direct contact with the receiving layer or in reception assignment such that a number of permeable colloid layers the layer in question separates from the receiving layer, as in multilayer material the case is. It is therefore understood that the creation of the diffusible color image by means of a light-sensitive layer that is "in contact" with an image-receiving layer is located, both a direct contact between the layers and an effective contact is understood, as in the latter case, when only the color image is able to to reach the receiving layer by diffusion in accordance with the image.

According to a preferred embodiment of the invention described above the formation of the diffusing dye image takes place in such a way that the image-receiving layer is with the emulsion layer containing the coupler for the whole or at least for the Is in contact for the majority of the time that color development is occurring. Under certain circumstances, however, it may also be desirable to add one or more emulsions use the desired coupler or a mixture of couplers of the classes A, B or C contain, and after exposure, the color development of the emulsion to be carried out essentially completely out of contact with the pickled receiving layer. In this case, the developed emulsion becomes shortly afterwards with the receiving layer brought into contact, which has been treated with one of the dressing agents described above, so that a color image is transmitted. Such a procedure is particularly advantageous, if the mordant for the image-receiving layer is one of the basic dyes common acidic pickling agents, such as phosphomolybdic acid, phosphotungstic acid, tannic acid or the like., is to be used. For this purpose, the non-diffusing coupler, which generates the transferable color image, in the case of class B couplers, one or more basic substituents, e.g. B. amino groups in non-coupling positions and have a removable ballast group in the coupling position. In the case of couplers of class A, the dye part in the coupling position must be one or more basic groups and the ballast group in a non-coupling position of the coupler contain. In the course of the color development one thus obtains a potentially diffusible one basic dye image, and by placing it in contact with an acidic stained layer brings, the transfer of the basic dye takes place.

The term "non-diffusing" in connection with dye intermediates, Color formers, coupler substances, etc. has always been in the field of above Color photography common meaning and denotes products that are practical for everyone Purposes in or through organic colloid layers such as gelatin, including the photosensitive material according to the invention do not migrate.

The expression "diffusible" or "diffusible" has the same reverse meaning. It is applied to products that have the property effective by colloid layers of the photosensitive material in the presence of non-diffusing ones Hike products as defined above.

Claims (7)

PATENT CLAIMS: 1. Color diffusion transfer photographic process, in which at least one light-sensitive image is used to generate at least one color image Material containing halogen silver emulsion layer is exposed, developed and with a receiving layer is brought into contact, characterized in that a such material is exposed and treated with an alkaline solution that, closely related to halogen silver, d. H. in or adjacent to each emulsion, a developer substance and a diffusion-resistant coupler substance containing either in the coupling position by a pre-formed dye or a coupler part and in at least one non-coupling position by a diffusion-proofing position Group or in a coupling position by a diffusion-proofing group and substituted in at least one non-coupling position by a solubilizing group is, and that at least a portion of the diffusible image dye that is in the treatment with the alkaline solution in the exposed parts of the emulsions has formed if it is the developer substance associated with the halogen silver a color developer substance optionally containing solubilizing groups or if the developer is a black and white developer acts by transferring the halogen silver remaining after the alkaline treatment in developable state and developing by means of an optionally solubilizing agent Color developing agent containing groups generated on an image-receiving layer is transferred; or that a corresponding material, its diffusion-resistant coupler substance has any structure, is treated in the same way, but with the color developing agent that is associated with the halogen silver or that of the Development of the remaining halogen silver made developable is used, must contain at least one solubilizing group. 2. The method according to claim 1, characterized in that a primary aromatic color developer Amino compound is used. 3. The method according to claim 1 or 2, characterized in that that in order to make the remaining halosilver developable, is exposed. 4th Color photographic material comprising at least one light-sensitive material on a support Halogen silver emulsion and, if appropriate, customary intermediate and / or protective layers for performing the method according to any one of claims 1 to 3, thereby characterized in that at least the developer substance or one of the claims 1 defined coupler substances are contained in each emulsion. 5. Material after Claim 4, characterized by three differently sensitized halogen silver emulsions. 6. Material according to claim 4 or 5, characterized in that it is used as a developer substance contains a black and white developer. 7. Material according to claim 4 or 5, characterized in that it contains, as a developer substance, a color developer substance, preferably a primary aromatic amino compound. B. Material according to one of claims 4 to 7, characterized in that it contains the developer substance in the form of a complex salt with sulfur dioxide. 9. Material according to one of claims 4 to 7, characterized in that it contains the Entwieklersubstanz in the form of a Schiff base. 10. Material according to one of claims 4 to 9, characterized in that it contains a coupler substance of the general formula Fb-Y-Cp-DR in at least one emulsion, wherein R is a stable bond, D to a non-coupling position of the coupler part Cp bonded diffusion-proofing group and Fb denotes a diffusible dye or coupler part and Y has the meaning defined in claim 12. 11. Material according to one of claims 4 to 10, characterized in that it contains a diffusion-resistant coupler of the general formula RY-Cp-DR 'in at least one emulsion, in which R' one through a stable Bin-Jung D to at least one non-coupling Position of the coupler part Cp is a bonded alkali-solubilizing group and R denotes a diffusion-proofing group which is bound by a cleavable bond Y to the coupling position of the coupler part Cp. 12. Material according to claim 10 or 11, characterized in that Y is one of the following bonds: - N = N -, - O -, - Hg -, 'CH - or = CH -, - S -, - SS- and where Z is the atoms required to complete a ring. References considered: U.S. Patents Nos. 2,647,049, 2,661,293, 2,673,800; Eder, "Handbuch der Photographie", 5th edition, 1903, part 3, pp. 844-845. A priority document was displayed when the registration was announced.