DE2163576C3 - Color photographic recording material and color photographic positive-negative process for the production of scene images and auxiliary images containing silver - Google Patents

Description

contains, where R ² is an alkyl group with 1 - 17 carbon atoms, R ³ is an alkyl group with 5 - Ϊ 7 carbon atoms, Z is a sulfur atom or the group - NHCO- and π is 1, 2, 3, 4 or 5 is

5. Recording material according to claim 4, characterized in that the auxiliary image recording Silver halide emulsion layer capable of being used as color coupler I-hydroxy-4- (5-nonanamido-13-benzimidazol-2-ylthio) -N- (2-n-tetradecyioxyphenyl) -2-naphthamide contains

6. Recording material according to claim 1, characterized in that there are three for recording color-forming scene image recording units capable of green, red and blue light, respectively each containing at least one silver halide emulsion layer and that the sensitivity the auxiliary image recording capable silver halide emulsion layer in the area of the spectrum in which the absorption curves for red and green or red and overlap blue light sensitive scene image recording units, 2-15 times less, than those of the corresponding adjacent scene image recording units when in the overlapping area is exposed.

7. Recording material according to claim 8, characterized in that the auxiliary image recording Silver halide emulsion layer capable of sensitizing 3-ethyl-5- (3-ethyl-2-benzthiazolinylidene) rhodanine contains.

8. Recording material according to claim 1, characterized in that the silver halide in the silver halide emulsion layer capable of auxiliary image recording has a grain size of 0.05-0.5 μm

9. Recording material according to claim 1, characterized in that the silver halide emulsion layer capable of auxiliary image recording contains 0.22-1.62 g of Ag in the form of silver halide per m ²

10. Color photographic positive-negative process for the production of scene images and auxiliary images containing silver, preferably sound tracks, in a photographic recording material, in which a photographic recording material consists of a layer support, at least one color-forming silver halide emulsion layer capable of recording scenes, one for Auxiliary image recording capable silver halide emulsion layer, and optionally intermediate and / or cover layers exposed imagewise to silver-containing scenes and auxiliary images with the help a color developing agent composed of an aromatic primary amine and one color coupler color developed and, after protection of the The invention relates to a color photographic recording material From a - optionally transparent - layer support, at least one for

is scene recording capable color-forming SiI-berhalide emulsion layer, one capable of auxiliary image recording, preferably soundtrack recording, optionally a sensitizing dye containing - silver halide emulsion layer, and optionally intermediate and / or top layer. The invention also relates to a color photographic positive-negative process for the production of Scenes and auxiliary images containing silver, preferably sound tracks, in a photographic record

i-, drawing material in which a photographic Recording material consisting of a layer carrier, at least one capable of recording scenes, color-forming silver halide emulsion layer, a silver halide layer capable of auxiliary image recording

j (i emulsion layer, as well as, if necessary, intermediate and / or cover layers exposed imagewise to silver-containing scenes and auxiliary images with the help of a a primary aromatic amine consisting of a color developing agent and a color coupler

) -, developed and, after protection of the developed in the auxiliary picture Silver is bleached versus bleaching and - if necessary at the same time - is fixed.

It is known, e.g. from FR-PS 9 12 605, color photographic recording materials with min-

4 (i least one capable of scene recording color-forming silver halide emulsion layer and one for auxiliary image recording, preferably Soundtrack recording, enabled to use silver halide emulsion layer. The colored scenes

■ π are usually based on the three-color system made from three subtractive dyes, one yellow dye for blue light, one purple dye for green light and a cyan dye for red light. The production

■ ίο the dye images can be according to different Methods are done.

So z. B. Color images are produced by the so-called color bleaching process. To carry out this procedure is a record

> -, material used in three separate layers, each of which is opposite a primary Color range of the visible spectrum is sensitized, in each case a preformed subtractive dye contains which, depending on the

Developing a latent photographic image produced silver is destructible.

Color photographic recording materials can also be used with three superposed silver halide emulsion layers, from

Η · -) dent.i each against a primary color range of the visible spectrum is sensitive and contain the color couplers that are oxidized when coupling with Developer compounds of the primary aromatic type

Scher amines form subtractive dyes, the color of which is complementary to the primary color ranges of the visible spectrum. Instead of being used in the silver halide emulsion layers, the color couplers can also be used in a developer bath. After the dye image has been produced , the silver that has developed and the remaining silver halide are removed from the areas, usually by bleaching and fixing or by bleach-fixing.

Optical motion picture soundtracks can be generated on the same recording material on which the scene image is generated. The optical sound tracks can be of different densities or different areas. The sound track itself can consist of dyes, dyes and silver, ι ■ -> of silver compounds, of silver and other metals or of silver alone. To detect the photocell which is used exclusively then used in Kinefilmprojektoren almost to the light passing through an optical soundtrack light, is "sensitive to electromagnetic radiation of a wavelength of about 700 nm nm with a peak sensitivity at about 800 am. 2 the the scene image producing Subtraktivfarbstoffe have a maximum absorption in the range from 400 to 2> 700 nm. As a result, the dyes are almost transparent to infrared radiation and have only a very small modulation effect on the radiation to which the photocell is most sensitive. so

The silver produced in the chemical reduction of a silver halide latent image is opposite the full spectrum of radiation, which varies from the ultraviolet through the visible to the infrared Area extends, uniformly opaque and acts as an excellent modulator for infrared radiation, to which the currently used photoelectric cells are most sensitive. Silver compounds, z. B. silver sulfide and with metals, e.g. B. Gold, tinted silver are for infrared radiation also more impermeable than acid dyes. It follows that optical sound recordings in Color motion picture films should preferably not consist of image dyes. Against the presence of subtractive However, there is no objection to dyes in addition to other substances of the specified type.

As mentioned above, the developed silver and the remaining silver halide must be removed from the scene areas of a color motion picture film after the color image has been created. On the other hand, have developed silver or silver compounds present in the Tonspurbezirken be betbehalten unchanged when there is a Farbkinefilm with a sound track of the preferred type mentioned are known several methods to add the silver to the Tonspurbezirke of FarbkmeGhnen during the bleaching and Föderens of the silver and remaining sber halide of the scene Buda districts. For example , it is known from US Pat. No. 19 73 463 and 21 13 329 to cover the sound track areas with a varnish following the creation of the scene and sound track images and before the removal of the Sflbers and Sflberhalogenids. The lacquer prevents the bleach solution from diffusing into the soundtrack areas. After the silver has been re-halogenated in the scene areas, the lacquer is removed with the aid of a suitable solvent and the silver halide is removed from the entire recording material.

Another known method of preserving the metallic silver in the soundtrack districts is in recording the scene and soundtrack images and turning the latent image obtained into metallic Developing silver. In the case of copy materials, the remaining silver halide is removed by fixing the all material removed. In the case of reversal materials, only the soundtrack areas are frozen followed by color reversal development. At this stage, both types of recording materials a sound track made of metallic silver that is free of residual silver halide. That metallic silver is then bleached into both the soundtrack and scene bud areas transferred to fixable silver salt. In the sound track districts, the silver salt is converted back to metallic silver, by applying a viscous, highly active developer, e.g. B. with the help of conventional known Strip treatment process. Then the existing in the scene design districts Silver salt removed by fixing.

Another, e.g. B. from US-PS 22 63 019 known One method of preventing the trace of silver from being removed is to remove the metallic silver to be treated with a solution that causes a gold tint. The gold-tinted metallic silver obtained is not removed during bleaching and fixing

Another, e.g. Example, from US-PS 32 43 295 known method is to treat the Tonspurbezirke of the recording material in strip form with a quaternary ammonium salt, the silver metal unbleichbar makes disadvantage of this method as well as to the method in which a viscous developing solution in strip form to the Sound track districts is applied, however, is that expensive special devices, e.g. B. so-called "strip treatment wheels" are required. Another disadvantage is that the process known from US Pat. No. 3,243,295 can only be used in the case of recording materials which contain color couplers dispersed in a coupler solvent, and the quaternary ammonium compounds known from US Pat. No. 3,243,295 are only comparatively weakly effective .

Another, e.g. B. from US-PS 22 86 747 known method for the preservation of the metallic silver in the soundtrack areas is to use a multilayer photographic recording material which during the chromogenic development in the upper layer forms a dye which can be reduced to a leuco dye, softer Siiberioficn is able to reduce to metallic silver. The developed strip shape Tonspurbezirke be treated with water and a Scbwefekfioxvd- gasatmosphire passed, the gas being absorbed nor b in the wetted clay and the absorbed gas reduces the dye to a Leocofarbstoff. The recording material is then passed through an Ammomak sulfide nitrate solution, the leuco dye reducing SQberionen to metallic suber, which is deposited in the recording material.

It is also known, e.g. from US-PS 2143787, to convert the Sober located in the soundtrack districts into compounds or complexes that one Resist exposure. Sober or Silver halide before bleaching in sub-sulfide

be convicted. The sulphide is not converted into a fixable silver salt during bleaching and thus remains even after fixing as silver sulfide. From US-PS 22 58 976 it is also known To use treatment solutions that contain both sulfide and iodine compounds, which convert the silver into compounds that are not removed during bleaching and fixing.

Another, e.g. B. from US-PS 22 35 033 known method for producing sound tracks is to apply a separate layer to the back of the support. Either side the recording material is then treated, without the other side, with the treatment solutions used to bring in contact.

However, all of the previously known methods have numerous disadvantages, e.g. B. the disadvantage that part of the recording material must be treated separately during the development process. Most widely used at the present time is that discussed using a strip treatment device Process in which a reagent is applied to the soundtrack areas in the form of a narrow edge strip. When using such a strip treatment device that must be protected from the action of the Treatment solutions used damp recording material are dried before passing through the Strip treatment device can be performed, which according to a known procedure a Has rotatable roller which is immersed in a viscous treatment solution, and this in the form of an edge strip on an edge of the recording material. The conditions under which this strip treatment t-r is critical. So is z. B. the for Treatment of a 16 mm recording material was used Strip treatment roll only 2.4 mm wide. If the role accepts insufficient amount If treatment liquid is applied, too little of it is applied to the recording material, resulting in inferior quality May lead to sound tracks. On the other hand, if the roller takes up too much treatment liquid, then it is the edge strip applied to the recording material is too wide and can form parts of the scene image areas cover. In this case, silver remains in the set design areas and causes deterioration the quality of the color image in these districts.

Another problem encountered with this streak treatment process is that, when the recording material vibrates, the viscous treatment liquid can flow into the scene areas, which also leads to the stated disadvantages is carried out, still so critical since £ the appearance of some sources of error is unavoidable Gelegentfidi, these imperfections are corrected by a partial post-treatment of the recording material. In other cases, however, the recording material is spoiled and must be discarded.

The object of the invention is the production of high quality scene scenes and FM image recordings, preferably soundtrack recording, start in a particularly simple and economical manner without separate treatment of the auxiliary areas.

This object is achieved by 1.) a color photographic recording material of the structure specified at the beginning, which is characterized in that the silver halide emulsion layer capable of auxiliary image recording

> a) has such a sensitivity that with image-wise Exposure of the silver halide emulsion layer (s) capable of recording scenes no image is generated in it, that it is b) a diffusion-resistant precursor compound of a

in silver bleach inhibitor that contains in the presence

an oxidized developing agent releases a silver bleach inhibitor which is a thiol or contains a selenol group and a hydrophobic group, and optionally

ιί c) that it contains another compound with a color developing agent consisting of an oxidized primary aromatic amine can react to color development,

. ·., And 2.) a color photographic positive-negative process of the type specified at the beginning, which thereby is characterized in that a recording material of the described for performing the method Features is used.

Recording materials with a silver halide emulsion layer, a mercaptan-releasing compound, namely a mercaptan-releasing compound Couplers containing are already known, e.g. B. from US-PS 32 27 554. In the case of the known recording

jo nung materials takes place the addition of a mercaptan releasing couplers for the purpose of releasing a development inhibitor.

Particularly advantageous photographic recording materials according to the invention are those which consist of multicolor cinema films with a soundtrack. Such recording materials consist of a transparent substrate on which several, in As a rule, three photographic units capable of recording scenes are applied, of which each has one or more, usually one or two, silver halide emulsion layers in such Wise arranged and sensitized that each unit is practically primary over another Color range of the visible spectrum is sensitive At any point there is also a soundtrack for recording certain photographic silver halide emulsion layers, due to their particular Sensitivity in scene-wise exposure of the scene-image recording layers, no image generated

The exposed photographic material is image recording unit having a group consisting of an aromatic primary amine Farbcniwicklcfvcfbindung to a scene image recording of silver and a non-diffusible dye in the scene or more Szenenbildaufzeichnungsemheiten, and a Hflfsbfldaufzeichnung of silver in the Hflfsschicht developed IKe oxidized color developing agent produced reacts with the A precursor compound of a bleach inhibitor present in the auxiliary layer with the release of a ballast group-bearing bleach inhibitor, which changes the bleaching of the silver in the πΐ1πη? ^ ΗΤΐΗΗ / ^ ΐττ ΐ ^ηηη ^^ " ^ ^τ ΐΓΚΤ ' ^η As a result of this development, the remaining silver becomes Halide and the silver that can still be removed by bleaching and fixing, whereby the silver present in the hoof layer is retained

130262/66

and represents the auxiliary image recording.

In addition to the units serving for the scene image recording and the layer for the auxiliary image recording The photographic recording materials according to the invention may have a yellow filter layer. s

The scene image recording layers of the photographic recording material according to the invention are intended to produce images consisting of subtractive dyes from the scene images to be recorded. The layers can form dyes whose color is complementary to that to which the layers are sensitive. So z. For example, the blue-sensitive layer produces a yellow dye image, the red-sensitive layer produces a cyan dye image and the green-sensitive layer produces a magenta dye image. Optionally, however, the layers can also be incorrectly sensitized, ie they can produce dyes whose color is not complementary to the color to which the layer in question is sensitive. If necessary, 2 ', these layers can be used to form a dye or dye mixture, the density appears to be neutral.

The recording materials according to the invention are both for use in negative-positive 2> System as well as for use in the inversion system.

To generate subtractive dyes, the recording materials are used in the presence of color formers developed, which in particularly advantageous κι Way consist of color couplers. As a rule, 5-pyrazolone couplers are used to form purple dyes, phenolic and naphtholic couplers for the formation of blue green dyes and overt Ketomethylene couplers used to form yellow dyes

In a particularly advantageous manner, each scene image recording layer contains a non-diffusible one photographic color coupler which reacts with oxidized color developing agent to form -ίο of a dye reacts. The dye formed in each of the layers is particularly advantageous Have a color that is complementary to the color of the wavelength range against which the the emulsion layer containing the color coupler is sensitized

However, the photographic recording materials according to the invention need not contain any couplers. In this case they are developed in baths which contain both diffusible developer compounds and diffusible color couplers. The oxidizing photographic developer compound couples with the diffusible color coupler to form a nondiffusible dye at the points where photographic silver halide development has taken place. B. from US-PS 22 52 718, 22 52 243 and 29 50 970 known

However, it has proven particularly advantageous to use non-diffusible couplers and to incorporate these into the silver halide emulsion layers intended for scene recording. Typical suitable, non-diffusible color couplers which can be incorporated into the silver halide emulsion layers intended for scene recording are, for example, the pyrazolone couplers described in US Pat of the type known from BE-PS 6 98 354, also the phenolic couplers of the type known from US-PS 23 67 531, 24 23 730, 24 74 293, 33 11 476, 34 19 390, 34 58 315 and 34 76 563 Type, as well as the open-chain ketomethylene couplers of the type known from US-PS 22 06 142, 24 36 130, 27 28 658 and 34 08 149 type. The layers may also contain other types of couplers, e.g. B. development inhibitor-releasing couplers such as are described e.g. B. from US-PS 32 27 554 are known.

Those present in the photographic material according to the invention for auxiliary image recording A capable silver halide emulsion layer can be arranged at any point on the recording material be. So she can z. B. be the layer closest to the substrate or it can be the front The layer support furthest away may be the layer, furthermore it can be between two scene image recording units be arranged, or between a scene image recording unit and a filter layer, if there is one.

Depending on the arrangement of the scene image recording units and auxiliary layers and any existing ones Filter layers are various exposure methods applicable to a scene image recording without a scene image being generated in the auxiliary layer at the same time. Is z. B. the auxiliary layer the light-sensitive layer closest to the support and is between this auxiliary layer and the scene image recording units have a removable, e.g. B. bleachable, filter layer arranged so the scene image recording layers can be seen from the emulsion side, and the auxiliary layer through the Layer support are exposed through.

On the other hand, if the auxiliary layer is the light-sensitive layer furthest away from the support and is located between the auxiliary layer and the underlying scene image recording layers a removable filter layer, the scene image exposure can pass through the support and the Auxiliary layer exposure take place from the emulsion side.

as a rule, however, it proves to be expedient to expose all layers from the emulsion side. In this case, selective exposure of auxiliary layer and scene image recording layers is achieved in that the auxiliary layer differs from the other layers with regard to photographic sensitivity or spectral sensitization or with regard to both properties. So z. B. the auxiliary layer to be sensitized to radiation to which the scene set recording layers are at least partially insensitive, z. B. against infrared radiation, the exposure taking place through suitable filters. Optionally, the auxiliary layer can be sensitized to the area located between two of the existing scene image recording layers with comparatively equal minimal sensitization. Such areas are present, for example, between the blue- and green-sensitive layers or the green- and red-sensitive layers of a color photographic recording material which has three color-forming units, each of which is primarily sensitized to a different primary region of the visible spectrum. In addition to or instead of the spectral sensitization, the auxiliary layer can have a different photographic sensitivity than the others

Have layers. So the auxiliary layer z. B. be insensitized, d. H. she can only do the one on the natural sensitivity of silver halide to radiation of the ultraviolet or near have sensitivity based on the blue spectral range. In this case the auxiliary layer should be less be more sensitive than the blue-sensitive layer, so that it is when the blue-sensitive layer is exposed The scene image recording layer is not exposed. Optionally, the auxiliary layer can be opposite to one of the primary color areas of the visible spectrum must be sensitized. In this case too, the auxiliary layer should be less sensitive than the scene recording layer which has a corresponding spectral Has sensitivity.

According to a particularly advantageous embodiment of the invention, the recording material contains three color-forming scene image recording units capable of recording green, iOtem or blue light, each with at least one silver halide emulsion layer and the sensitivity of the silver halide emulsion layer capable of auxiliary image recording in the region of the spectrum in which the The overlap absorption curves of the scene recording units sensitive to red and green or red and blue light is 2-15 times smaller than those of the corresponding neighboring scene recording units when exposure is carried out in the overlapping area.

In a color photographic recording material with more than one light-sensitive layer, each layer is practically sensitized to a different primary color range of the visible spectrum, ie to the blue range from about 400 to 500 nm, to the green range from about 500 to 600 nm or to the red range from about 600 to 700 nm, whereby the sensitization of the individual layers can overlap to a certain extent. For example, the sensitization of a first layer can gradually decrease at a wavelength at which the sensitization of the second layer begins. At some points in this area of overlapping sensitization, the sensitization effect in the two layers is very close to a minimum. The indicated auxiliary layer can be sensitized in such a way that it is at least sensitive to such an area of minimal sensitization. If the auxiliary image recording is copied, the exposure takes place with light of a narrow bandwidth, the maximum intensity of which lies in the specified range of minimum sensitization between two color-forming units.

In a multilayer material having three color-forming units, each of which is sensitized to a different primary color region of the visible spectrum, such a region of minimal sensitization occurs between the blue and green regions of the visible spectrum. Depending on the type of sensitizing dyes used in the blue- and green-sensitive color-forming units, the point of minimal sensitization is usually between about 460 and 500 nm. In the case mentioned, another such region occurs between the green and red regions of the visible spectrum. The point of minimal sensitization is in this case between about 550 and 590 nm, again depending on the type of sensitization used in the green and red sensitive colored units.

dyes.

The layer intended for auxiliary image recording which is minimal compared to at least one such area Sensitization is sensitive, must also have a photographic sensitivity exhibit which is at least 2 times less than the photographic of the two color-forming units of adjacent ones spectral sensitization. This is necessary because the sensitization of the auxiliary layer Sensitizing dyes used in relation to the specified areas of minimal sensitization neither lead to a sharp drop in the sensitization of the silver halide grains. These dyes lead therefore to a sensitization of the auxiliary layer, which is related to the sensitization of the color-forming units neighboring spectral sensitization overlaps. To avoid exposure of the auxiliary layer during the scene-image-wise exposure of the color-forming units capable of scene image recording therefore, the auxiliary layer must have a sensitivity lower than that for scene image recording certain color-forming units with adjacent spectral sensitization.

The layer capable of auxiliary image recording is preferably by means of a sensitizing dye sensibilisieri, which leads to a peak sensitization approximately in the area of minimum sensitivity, which is between the sensitizations of two color-forming units of neighboring spectral sensitization, leads. Since the peak of sensitization occurs in this area of minimal sensitization, the spectral falls Sensitization and thus the photographic sensitivity of the auxiliary layer to light from wavelengths lying on the two sides of this point gradually from. Conversely, the spectral sensitization and thus the photographic sensitivity increases of the color-forming units of neighboring spectral sensitization to light of the same wavelength gradually in the direction of their respective sensitization peaks. It thus follows that the spectral Sensitization and the photographic sensitivity of the I mfschichi almost maximum in that Area of minimal sensitization of the color-forming units with neighboring spectral sensitization whereas the spectral sensitization and photographic sensitivity of these color-forming units decreases In this area of minimal sensitization, therefore, are the photographic sensitivity of the two color-forming units and the photographic sensitivity of the auxiliary layer as far as possible the same.

The "photographic sensitivity" of a silver halide emulsion layer or color-forming unit is understood to mean the photographic sensitivity of this layer or unit at the wavelength or wavelengths of light used for exposure, but not the maximum photographic sensitivity of the layer or unit which may possibly be at other wavelengths of light.

Typical suitable sensitizing dyes which are used to sensitize the auxiliary layer to a typical area of minimal sensitization. which lies between the peak sensitivities of the blue- and green-sensitive color-filling units capable of recording scenes are usable. B. 3-Ethyl-5- (l-ethyl-4 (lH) pvridylidene) -rhodanine, 3-ethyl-5- (3-ethy] -2-benzothiazoiinylidene) rnodanine and anhy-

dro - ^ '- bis - ^ - carboxyäthylJthiazolmocarbocyaninhydroxyd. The first two dyes mentioned are z. B. from »J. At the. Chem. Soc. ”Volume 73, (1951), page 5326

According to a particularly advantageous embodiment, According to the invention, the silver halide emulsion layer capable of auxiliary image recording contains 3-ethyl-5- {3-ethyl-2-benzthiazolinylidenj-rhodanine as the sensitizing dye.

A sensitizing dye that is used to sensitize ι ο of the auxiliary layer compared to a typical area of minimal sensitization, the one between the peak sensitivities of the green and red sensitive ones Scene image recording capable, color-forming units is usable, is z. B. Anhydro-3 ', 9'-diethy 1- S-methoxy-S-phenyl-S-ß-sulfobutylJoxaselena-carbocyanine-hydroxyd.

The silver halide content of the auxiliary layer can be different. According to an advantageous embodiment of the invention, the silver halide emulsion layer capable of auxiliary image recording contains 0.22 to 1.62 g of Ag in the form of silver halide per m ² . Since the amount of silver halide present in the auxiliary layer has an influence on the turbidity of the recording material and the sharpness of the image, it has proven to be particularly advantageous to use the silver halide in the auxiliary layer in such amounts that about 0, ^{per m 2 of support surface} 27 to 1.1 g, in particular about 032 to 031 g, of silver in the form of silver halide are omitted. Very particularly advantageous auxiliary layers contain about 0375 to 0.81 g of silver in the form of silver halide ^{per m 2 of support surface.}

The grain size of the silver halide present in the auxiliary layer can also be different.

According to an advantageous embodiment of the invention, the silver halide has a silver halide emulsion layer capable of auxiliary image recording a grain size of 0.05-0.5 μπ>.

Especially in those cases in which the auxiliary layer is used to record the soundtrack image of a motion picture film is used, the grain size should be as small as possible without exposing the soundtrack areas to light of so high intensity that the scene image recording layers in the soundtrack areas are overexposed. The use of silver halide having a grain size of about 0.05 to 0.2 microns has been found to be particularly advantageous.

To produce the auxiliary layer, negative developable emulsions and fogged direct positive emulsions with conventional silver halides, z. B. silver chloride, silver bromide, silver chloride bromide, Silver bromide iodide, silver chlorobromide iodide or mixtures thereof can be used.

Particularly advantageous results can be achieved when using a reversal recording material with an auxiliary layer of a fogged, direct-positive silver halide emulsion of the type known from FR-PS 15 20 821. Such fogged direct positive emulsions are uniformly fogged. The latent image generated in the layer is then destroyed in direct proportion to the exposure. During development in conventional black-and-white developers, a reversal image is generated, the density of which is inversely proportional to the exposure, i.e. the greatest density is in the unexposed areas _h) and the lowest density occurs in areas of strongest exposure. The use of such direct positive emulsions has proven to be particularly advantageous for the generation of a super-soundtrack recording in reversal materials, since the soundtrack recording is from a negative original can be copied instead of a positive original. It is known that soundtrack recordings obtained from negative originals are of better quality than soundtrack recordings obtained from positive originals. The use of fogged direct positive super halide emulsions in the auxiliary layer of Reversal materials therefore result in the formation of the higher quality negative soundtrack recordings.

The silver covering power of the silver image formed in the auxiliary layer of reverse kinematic materials can be determined by image-wise retention of silver originating from an adjacent silver halide emulsion layer, the silver reduction thereof independently from the exposure is to increase. Preferably acts the auxiliary layer is a direct positive emulsion layer and the adjacent one Silver halide emulsion layer around a fogged or unfogged layer of a Lippman emulsion.

Direct-positive superhalide emulsions can also be used to produce the auxiliary layer which a latent image is mainly generated in the interior of the silver halide grains. Such emulsions are e.g. B. from US-PS 25 92 250 known Such emulsions of the inner grain image type can be in Develop the presence of a fogging developer such as a hydrazine compound developer. The silver halide emulsion layers present in the color-forming units of recording materials with such auxiliary layers also consist of emulsions of the inner grain image type, when direct positive color images are to be produced. The scene image recording areas of the auxiliary layer must be flash exposed in order to prevent the development of the silver halide present in these areas and the subsequent release of bleach inhibitor, which leads to the prevention of the This developed silver would fade.

According to a particularly advantageous embodiment of the invention, the silver halide emulsion layer capable of auxiliary image recording contains a hydroquinone or a color coupler as a precursor compound, which releases a silver bleach inhibitor in the presence of an oxidized developing agent

Bleach inhibitor releasing couplers, hereinafter referred to as "BIR" compounds or couplers as well as other useful bleach inhibitor releasing compounds that are not Couplers are described in more detail later.

As a rule, the amount of bleach inhibitor releasing compound (BIR compound) which is required to react with all of the oxidized color developing agent which would be formed during the complete development of the silver halide present in the auxiliary layer is greater than the amount which is required is required to release as much bleach inhibitor as is needed to fully protect the developed silver from fading. Bleach inhibitors certain type can, when n "be an amount exceeding the amount required for completely contactors of the developed syllables over fading cause adverse effects, 7 for example, a deterioration of the fixing, inhibit the development of unwanted reaction with oxidized color developing agent or diffusion too developing

silver that should not be protected by a bleach inhibitor It is therefore advisable if the auxiliary layer contains about the same amount of BIR compound which releases a sufficient amount of bleach inhibitor to record all of it in the audio track. developed silver to protect practically completely. That amount of BIR connection is there less than the amount required to cope with the whole in developing the whole in the auxiliary layer existing silver halide to react oxidized color developing agent.

For these reasons, it has proven to be advantageous to use the auxiliary layer in addition to the BIR connection Incorporate scavenger for oxidized developer compound. The combination of interceptor and BIR compound should be present in at least such an amount as is necessary in order to be able to withstand the whole of the Development of all the silver halide present in the auxiliary layer, formed by oxidized color respond to developer connection. The scavenger is expediently used in an amount which is around one Several times greater than the amount of BIR compound. So is z. B. the one present in the auxiliary layer Amount of scavenger often 4 to 10 times greater than the amount of BIR compound present in that layer.

As a reference point may further serve that about 100% of the developed silver can be retained in general, if about 0.01 to 0.03 milli- j _U mole one having a ballast group silver bleach inhibitor is provided in the development of an auxiliary layer containing per m ² Support surface contains about 750 mg of silver in the form of silver halide with an average grain size of about 0.1 micron, are released.

The scavenger for oxidized developing agent may e.g. B. of a hydroquinone, e.g. dioctyl hydroquinone, or a competing photographic coupler. A “scavenger” is any compound that reacts with oxidized developer compound and in this way prevents the oxidized developer compound from migrating from the development site, and which furthermore does not release a bleach inhibitor. If the oxidized color developing agent were to migrate away from the point at which development took place, it could with a color coupler at another point, e.g. B. react in one of the scene image recording units of the recording material to form a dye. The production of such a dye at a location remote from the color development site would result in a wrong color tone in the developed image. It thus follows that the auxiliary layer should contain the scavenger for oxidized developing agent and the BIR compound at least in such an amount that is sufficient to combine with all of the oxidized color developing agents which are formed during the development of all of the silver halide present in the auxiliary layer react. _w ,

Optionally, the BIR compound and the competing coupler used as a scavenger can be used be of the same type of coupler.

Is z. For example, if the BIR coupler is a 5-pyrazolone coupler, the competing coupler can also be a 5-pyrazolone _b $. However, it can also be couplers of other types, e.g. B. phenolic or open-chain ketomethylene couplers. The dyes which are produced in the reaction of BIR and competing couplers therefore do not necessarily have to have the same hue. The dyes can be diffusible if they can be washed out of the recording material without practically staining any point, be it the soundtrack or the scene image recording areas. Otherwise the dyes formed from the BIR compound and the competing coupler should be nondiffusible.

If a scavenger for oxidized developing agents is used, its reaction rate with the oxidized color developing agent should preferably be about the same as that the BIR connection. This "adjustment" of the rate of reaction with oxidized color developing agent is done to ensure that the appropriate amount of bleach inhibitor is released. Is this Scavenger is less reactive than the BIR compound, so the majority of the BIR compound reacts with the oxidized color developing agent before the scavenger is reacted. In this case most of the bleach inhibitor is in released at an early stage of development in which there is still very little developed silver, to which the bleach inhibitor can be absorbed. On the other hand, is the scavenger more reactive than the BIR coupler, almost all of the silver halide must be developed before the BIR compound with oxidized color developing agent is released If a bleach inhibitor does not react, therefore, an almost complete exposure and development of the in the If the silver halide present in the auxiliary layer has taken place, the developed silver is not protected by the bleach inhibitor and is consequently removed during the subsequent bleaching and fixing step

The auxiliary layer is thus advantageously made up of a mixture of BIR compound and scavenger (for which z. B. may be a connection not consisting of BIR couplers) incorporated BIR compound and scavenger are selected so that they are practically the same speed as the oxidized Color developing agent react. A competing coupler is preferably used as a scavenger which is capable of producing a nondiffusible blue-green dye which is at least absorbs a certain part of a radiation of over about 700 nm and in this way to that by the Auxiliary silver image contributes to the infrared density.

Both the BIR compound and the scavenger can be incorporated into the auxiliary layer by a wide variety of customary known methods. One method uses known organic solvents as the coupler solvents. at these coupler solvents can be low-boiling or water-soluble solvents, which can be removed from emulsions by evaporation or washing out as soon as the solvent and the compound dissolved therein are dispersed in the emulsion. High boiling point organic crystalloidal coupler solvents can also be used remain in the emulsion. Typical suitable solvents are for example from US-PS 28 01 170, 28 61 170, 28 01 171, 29 49 360 and 23 22 027 are known.

Conventionally known photographic hydrophilic colloids, e.g. B. gelatin, can be used.

The recording materials according to the invention can be processed in conventional developing devices, e.g. B. in continuously operating development devices. The processing temperatures can be different. In conventional manner they are about 20 to 60 ° C temperatures of 25 ⁰ C, 40 ⁰ C and 5O ⁰ C have been found to perform high-speed developing method to be suitable.

The exposure of the auxiliary image recording specific layer can be done before, simultaneously with or after the scene exposure. the The auxiliary layer is exposed in such a way that the Auxiliary image, e.g. soundtrack image, at least in the auxiliary layer is recorded. Following the exposure, the recording material is processed as indicated

Although the recording materials according to the invention are particularly advantageously suitable for the production of color motion picture films with a silver-tone track recording, they are, however, also suitable for other types of color photographic materials with an auxiliary image recording. to the example of a Farbkinefilmes be explained in more detail with the processing of the Silbertonspuraufzeichnungen Aufzeichnungsma- y <terials.

The processing of an exposed negative-positive photographic recording material, its scene image recording layers Contain couplers, jo can be carried out as follows:

After exposure, the photographic material is developed using a primary aromatic amine color developing agent. The oxidized color developing agent formed in the auxiliary layer reacts with existing photographic couplers. If these are competing couplers, only dyes are produced. The bleach inhibitor precursors present, on the other hand, react with the oxidized developing agent to produce a bleach inhibitor which is adsorbed by the developed silver. In the scene recording units, the oxidized color developing agent reacts with existing couplers to produce nondiffusible dyes. After development has ended, the scene image recording units contain silver plus nondiffusible dyes, and the auxiliary layer contains silver (and dyestuff if a nondiffusible dyestuff was formed during development) to which the bleach inhibitor is adsorbed. When the recording material is now treated in a bleach-fixing bath or a bleaching bath, the whole, is not protected by the bleach inhibitor developed silver is converted into a v> fixable salt and removed from the recording material. In the auxiliary layer, the silver is protected by the bleach inhibitor and cannot be bleached, which is why it is not removed from the recording material. After bleaching and fixing or bleach-fixing, the recording material contains nondiffusible dyes in the scene image recording units and silver (and dye if a nondiffusible dye was formed during development) in the auxiliary layer.

The bleach inhibitor released from the bleach inhibitor precursor compound during development can either be resistant to diffusion or moderately diffusible. If it is resistant to diffusion, it does not migrate and is adsorbed on the spot by the silver present there. In this case, only that in the Auxiliary layer developed silver protected by the bleach inhibitor, and this silver is therefore the only one However, silver which remains in the recording material after bleaching and fixing is the one formed Bleach inhibitor is moderately diffusible, so it can migrate away from the place of its formation and from developed Silver, which is present elsewhere on the recording material, are adsorbed. There photographic silver halide emulsion layers in color photographic recording materials extreme are thin, however, the pronounced migration is migration from one layer to another, but not the lateral migration within a certain layer If the anti-seizure inhibitor is therefore moderately diffusible, so it diffuses out of the auxiliary layer and into those arranged above or below the auxiliary layer Layers. If there is developed silver in these adjacent layers, the bleach inhibitor becomes adsorbed by this silver, which is also made unbleachable in this way.

The arrangement of a silver halide emulsion layer capable of auxiliary image recording on a multilayer photographic recording material increases, as already mentioned, the haze or the Fogging of the recording material and reducing the sharpness of the scene image when the exposure takes place through the auxiliary layer. This effect is due to light scattering caused by the in the Auxiliary layer present silver halide body is effected. The greater the silver halide content this Layer, the greater the light scattering and, consequently, the greater the loss of sharpness the silver halide content of the auxiliary layer should therefore be low for image sharpness. A reduction in the However, the silver halide content of the auxiliary layer reduces the silver density of the developed sound track and eventually reaches a point where the density is insufficient for excellent results throughout the life of the footage. At this point it is still possible additional improvements in the sharpness of the scene by further lowering the silver halide content to achieve the auxiliary layer. The silver density required for the sound track can be achieved in this case when the soundtrack exposure is carried out in such a way that the adjacent to the auxiliary layer arranged scene image recording units are exposed and that formed during development Bleach inhibitor is moderately diffusible, so that it can be incorporated into these adjacent scene recording units migrate and be adsorbed by the silver developed in these units. After bleaching and fixing, the recording material then contains a scene image recording Dye that is practically free of silver, as well as a soundtrack recording of silver in both the auxiliary layer as well as in the adjacent scene image recording units.

The color photographic recording materials according to the invention can have intermediate layers between the individual units, the compounds may contain those with oxidized color developer compounds be able to react. Such compounds are usually used as a scavenger for denotes oxidized color developing agents and

are incorporated into the intermediate layers to prevent migration of the oxidized color developing agent from the development site located in one layer to an adjacent layer, where the developer compound could react with a coupler present there to form a wrong color shade avoid typical suitable such scavengers are z. B. octylhydroquinone, dioctylhydroquinone, p-aminophenols, hydrazines, ascorbic acid derivatives and compounds of other types, such as those described e.g. B. from US-PS 24 03 721, 26 75 314, 23 56 486, 23 60 290, 27 01 19 /, 27 04 713, 27 28 659, 27 32 300 and 27 35 765 are known. It was found to be moderately diffusible Bleach inhibitors through interlayers containing such scavengers into adjacent silver halide emulsion layers migrate and adsorbed by the silver developed there in the specified manner can be.

Instead of the color photographic recording material To subject it to a direct color development 2 »it can also be a reverse development with the following Process stages are subjected to:

1. black and white development,

2. Treatment with an intermittent bath,

3. Color development of the remaining, undeveloped, fogged silver halide,

4. Treatment with intermittent bath and

5. Bleach-fix or bleach and fix.

Shall be a reversal material for making a motion picture film are used with a silver-tone track, then the auxiliary layer in the scene design districts must be veiled so that it is fully developed during black and white development. This measure takes place about any development and the resulting bleach inhibitor formation in the production design districts of the r> Avoid auxiliary layer during color development as it is undesirable to use silver in the scene design areas of the material to be retained.

_{The 4} n BIR compounds which can be used in a particularly advantageous manner as precursor compounds of bleach inhibitors are couplers which, apart from the bleach inhibitor component, can consist of any residue which has an active site that is capable of reacting with an oxidized one primary aromatic amine _{is capable of being 4} -, standing color developing agent and can be substituted at this active site by a radical forming a bleach inhibitor, and which retain their reactivity towards oxidized color developing agents if they are substituted in the specified manner. Residues of photographic couplers have proven to be particularly advantageous, e.g. B. remnants of 5-pyrazolone couplers, of phenolic couplers including oc-naphthol couplers and of open-chain ketonmethylene couplers η learn. If the couplers are substituted in the coupling position by a radical which forms a bleach inhibitor, they represent what are known as BIR couplers. If the radical is not a coupler radical, BIR compounds are present.

A diffusion-resistant precursor compound t, o of a bleach inhibitor is to be understood as a compound which meets the following requirements: is the compound of a veiled gelatin-silver chlorobromide emulsion, which is about 80 molar with respect to chloride and 20 molar with respect to bromide, incorporated, and b ^r > the emulsion obtained is applied to a cellulose triacetate support in such a way that ^{1.5 g of gelatin and 0.75 g of silver are used per m 2 of} support surface, and the emulsion layer obtained also contains a scavenger for oxidized developer compounds, which is practically the has the same reactivity with oxidized developing agent as the precursor compound, the total amount of precursor compound and scavenger present being sufficient to react with practically all of the oxidized developing agent formed during development, and the recording material is treated with a color developer of Example 1 below damn developed rubbed composition, so, if the precursor compound is present in an amount sufficient to form in the reaction with oxidized developing agent per m ² of support surface about 0.054 bleach inhibitor to 1.1 millimoles ballasted group, a nm at 900 measured infrared density of obtained at least 0.80 when the developed silver is treated for 90 seconds at a temperature of 25 ° C with a bleach-fix solution of the following composition:

NaFeEDTA +) (13% Fe) 60 g Na.SO ₃ 12 g NH ₄ SCH 12g Na ₄ EDTA +) 7g Ammonium thiosulfate 200 ml (6O% solution) Topped up with water 1 liter PH value 6.68

+) EDTA = ethylenediaminetetraacetic acid.

In performing the indicated test, the weight ratio of competing coupler becomes Precursor compound chosen so that the optimal amount of bleach inhibitor under the specified conditions is released.

The hydrophobic group of the bleach inhibitor released from the precursor compound can e.g. 3rd one be medium to long chain alkyl group. One task of this group is to act as a ballast group, with whose help the rate of diffusion of the silver bleach inhibitor in the hydrophilic colloid of the silver halide emulsion layers of the recording material is controllable.

Typical compounds of this type which are suitable as bleach inhibitors are e.g. B. by a thiol or selon group substituted alkanoic acids, in particular 2-mercaptoalkanoic acids, by a thiol or selenol group substituted aryls provided with ballast groups, e.g. B. alkyl and alkylamidothiophenols and thionaphthols, ballasted heterocyclic groups containing a thiol or selenol group Compounds with at least one nitrogen atom, e.g. B. Alkylamidomercaptobenzoxazole, Alkylamidobenzothiazole, Alkylamidomercaptobenzimidazole, Alkylamidomercaptothiadiazole, Alkylthiomercaptothiiidiazole, Alkylamidomercaptotriazoles, 1-alkylamidophenyl-5-mercaptotetrazoles and ballasted mercaptoquinolines, e.g. B. Alkylamido and Aikylmercaptoquinolines, as well as ballast groups Thiocarboxylic acids, e.g. B. alkyl and alkylamidothi benzoic acids.

According to a particularly advantageous embodiment of the invention, the silver halide emulsion layer capable of auxiliary image recording contains a color coupler which, in the coupling position, contains a group of the formula - X - A ¹ - Rj, in which

X equals a sulfur or selenium atom,

A ¹ equals a carbonyl group, thiocarbonyl group, carboxymethylene group, a 3-membered carbocyclic ring with two free bonds or a 3-membered heterocyclic ring - with at least one carbon atom, one nitrogen, oxygen, sulfur or selenium atom and two free bonds,

R ¹ equals a halogen atom, a nitro group, an optionally substituted alkyl group, an optionally substituted aryl group, an alkylthio group, a carboxyalkylthio group, an arylthio group, an alkylcarbonylalkylthio group, an alkylcarbonylarylthio group, an arylcarbonylarylthio group, in which the specified substituent group, derhippcituenteno, an | -, aryicarbonylalkylthio group thio 3-22 carbon atoms, an amide group having 4 to 22 carbon atoms, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group j _0, an aryloxycarbonyl group, a carbamoyl group, an alkoxy group or an aryloxy group and

a is 0, 1,2, 3, 4, 5 or ö, with the proviso that R ¹ is not alkylcarbonyl group, arylcarbonyl group, ₂ -, Aikoxycarbonylgruppe, aryloxycarbonyl group, carbamoyl group or amide group having 4-22 carbon atoms, when A ¹ represents a carbonyl - or thiocarbonyl group, where the group - A ¹ -R] has a molecular weight of 125; to 100, and where a hydrophobic, diffusion-proofing group is bonded ^{to A 1 when A 1 is} a 3-membered, carbocyclic ring with two denotes free bonds or a 3-olefin heterocyclic ring with at least one carbon atom, at least two nitrogen, oxygen, sulfur or selenium atoms and two free bonds.

Typical three-membered carbocyclic rings which A ¹ can represent are, for example: Cycloalkylene rings, e.g. B. Cyciopropyien-, Cyciobutyien-, Cyciopentyien- or cyclohexylene rings, cycloalkylene rings, z. B. Cycloprcpenylene, cyclobutenylene, cyclopentenylene, cyclopentadienylene, cyclohexylene or cyclohexadienylene rings or arylene groups, e.g. B. phenylene, naphthylene or anthrylene groups.

If A ^{1 is} a 3-membered heterocyclic ring, this is preferably 5- or 6-membered. Typical heterocyclic rings are, for example: oxirenyl, furanyl. Benzofuranyl, isobenzofuraayl, diber.zofurany! -, Qxazeiy! -, benzoxazoly! -,! Soxazolyl-, benzisoxazolyl-, oxadiazolyl-, benzoxadiazolyl-, 1,2-pyranyl-, 1,4-pyranyl-, 2 (K ) Benzopyranyl-, 4 (H) -Benzopyranyl-, dioxolyl-, methylenedioxybenzene-, l ^ -oxazinyl-.l ^ -oxazinyl-.l. ^ Oxazinyl-. Morpholinyl-, 13-dioxolanyl-, 13-oxathianyl-, 1 , 4-OxatManyl-, 1,2-Dioxanyl-, 1,3-Dioxanyl-, 1,4-Dioxanyl-, Dioxanenyl-, Dtoxadienyl-, Diacetyl-, Pyrrolyi-, Indolyi-, Isoindoiyl-, Carbazoryl-, Pyrrocolinyl- , Acridinyl, phenanthridinyl, eo 2-imidazolinjl, 3-imidazolinyl, 4-iniidazonnyl, pyridyl, pyridazinyl, cmnolinyl, phthalazinyl, quinoxalinyl, pyrimidinyl, pyrazolo [3,4d ^> yriniidinyl- , Hypoxanthinyl, benzopyrimidinyl, pyrazinyl, chmoxafinyl, phthalazinyl, quinoknyl, isoquinolinyl, phenazmyl, phenoxazinyl, phenothiazinyl, peninyl, pteridinyl, 13 ^ -triazinyl, lA4-TWazinyl, lÄSinyl Triazinyl, triazolyl, benzotriazolyi, tetrazolyl, triazinthionyl, l (H) azepinyl, piperidinyl, imidazolidinyl, Quinolizidinyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, thiadiazolyl, benzothiadiazolyl, 1,2-dithiolyl, 1,3-dithiolathiolyl, 13- -, thianthrinyl, thiamorpholinyl, 1,4-thianinyl, 1,4-dithianyl, 1,4-dithiadifcnyl, selenazolyl, benzoselenazolyl, isoselenazolyl, benzisoseleaazolyl, selenadiazolyl and benzoselenadiazolyl rings.

If Ri stands for an optionally substituted alkyl group, it has 1 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and consists, for. B. from a methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, isoamyl, tert-amyl, cyclopentyl -, Hcxyl, Cyclohexyl, Cyclohsxsdienyl-, Heptyl-, Ociy! -, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl or octadecyl group or a haloalkyl group, z. B. a fluoroalkyl, chloroalkyl or bromoalkyl group, for example a chlorooctyl, bromodedecyl or fluorotetradecyl group or a sulfoalkyl group, e.g. B. a sulfohexyl, sulfooctyl or sulfododecyl group or a sulfatoalkyl group, e.g. B. a sulfatodecyl or sulfatotetradecyl group or an alkylsulfonylalkyl group, e.g. B. an ethylsulfonylbutyl group or a cyanoalkyl group, e.g. B. a cyanohexyl, cyanooctyl or cyanodecyl group or a carboxylalkyl group, e.g. B. a carboxyhexyl, carboxydecyl or carboxyhexadecyl group or an aralkyl group, e.g. B. a benzyl, phendodecyl or tolyldodecyl group or an alkoxyalkyl group, e.g. B. an octoxyhexyl, butoxyhexyl or ethoxydecyl group or an aryloxy alkyl group, e.g. B. a phenoxymethyl or phenoxyethyl group or an alkoxyaralkyl group, ζ. Β. a methoxyphenylmethyl or butoxyphenylhexyl group or an acyloxyalkyl group, e.g. B. a benzoyloxy hexyl or acetoxybutyl group or an alkoxycarbonylalkyl group, e.g. B. a butoxycarbonylhexyl group or an aryloxycarbonylalkylgnippe, z. B. a Phenoxycarbonyläthyl- or Chlorophenoxy carbonvibutylgruppe or an Alkylamidoalkyigruppe, z. B. a hexanamidobutyl or octanamido propyl group or an arylamidoalkyl group, ζ. Β. a phenylamidoethyl or methylphenylamido butyl group.

If R ^{1 stands} for an optionally substituted aryl group, this can optionally have fused aromatic rings and consist, for example, of: phenyl, naphthyl, anthracenyl or phenanthrenyl groups or a haloaryi group, e.g. B. a ChksrphenyK trichlorophenyl. Dibromophenyl, fluorophenyl or chlorotolyl group or a sulfoaryl group, for example a sulfophenyl group or a sulfatoaryl group, e.g. B. a solfatophenyl group or a nitroaryl group, for example a nitrophenyl or dinhrophenyl group or a cyanoaryl group. for example a cyanophenyl or cyanonaphthyl group or a carboxyaryl group, for example a carboxyphenyl or dicarboxyphenyl group or an alcaryl group, ζ. B. a ToIyI-, Butyiphenyl-, Decylphenyl-, Dütnyiphenyl- or Triflnormegroppe oda an aralkaryl group, eg an eihenyl- oda Naphtfaieifaenylgnippe or an AOmxyaryigrappe, z. B. an octaxyphenyl or mphenyl group; an arykixyaryl nipple, ζ. & enter phenoxy · phenyl or phenoxynaphthyl group; an acykxyaryl group, e.g. B. a Benzoytoxyphenyl- or Acetyl-

oxyphenyl group; an alkoxycarbonylaryl group, e.g., an ethoxycarbonylphenyl group; an aryloxycarbonylaryl group, ζ. B. a phenoxycarbonyl · phenyl or methylphenoxycarbonylnaphthyl group; an alkylamidoaryl group. z. B. an acetamidophenyl, Amylamidophenyl, di-t-amylamidophenyl, Hexanamidophenyl, heptanamidophenyl. Octanamidophenyl, Nonanamidophenyl, decanamidophenyl, undecanamidophenyl, dodecanamidophenyl, tridecanamidophenyl, Tetradecanamidoaryl ·, Pentadecanamidophenyl ·, Heptafluorobutanamidophenvl- or Carboxycyclopentane acetamidophenyl group or a cycloalkyliminosulfonylaryl group, e.g. B. a piperidinylsulfonylphenyl, Azetidinylsulfonylphenyl-, pyrrolidinylsulfonylphenyl- or indolinylsulfonylphenylgrappe.

Typical thio groups for which R ^{1 can} stand are, for example: propylthio, hexylthio. Octylthio, dodecylthio, carboxybutylthio, carboxyhexylthio, phenylthio, naphthylthio, methylphenylthio, methylcarbonylethylthio, butylcarbonylpropylthio, methylcarbonylphenylthio, hexylcarbonyltolylthioyl or phenylthiothiophenylphenyl, benzylcarbonylphenyl.

If R ^{1 stands} for an amide group, this can for example consist of an alkylamido group. z. B. a hexanamido, heptanamido, octanamido, decanamido or heptafluorobutanamido group, an arylamido group, e.g. B. a benzylamido group, an alkarylamido group, e.g. B. a methylbenzylamido, butylbenzylamido, hexylbenzylamido or decylbenzylamido group, an aralkylamido group, e.g. B. a phenacetamido, phenbutanamido or tolylhexanamido group or an aryloxyalkylamido group, e.g. B. a phenoxyacetamido, naphthoxyacetamido or di-t-amolphenoxyacetamido group.

Typical carbonyl groups for which R ^{1 can} stand are, for example: butylcarbonyl, heptylcarbonyl, phenylcarbonyl, naphthylcarbonyl, ethoxycarbonyl. Butoxycarbonyl, phenoxycarbonyl and naphthoxycarbonyl groups.

Stands R ^! for a carbamoyl, alkoxy or aryloxy group, these can for example consist of: alkylcarbamoyl groups, e.g. B. butylcarbamoyl or hexylcarbamoyl groups, arylcarbamoyl groups, e.g. B. phenylcarbamoyl or naphthylcarbamoyl groups, furthermore ethoxy, butoxy, octoxy or benzoxy groups or phenoxy or toluoxy groups.

The group - A ¹ --RJ preferably has a molecular weight of 175 to 400. The group also preferably has no more than one solubilizing group, ζ. B. carboxy group. unless the group contains a hydrophobic component, e.g. B. has a long-chain alkyl group or an aryl group.

The hydrophobic, diffusion-proofing group bonded to A ¹ can consist, for example, of the atoms required to complete a 5- or 6-membered carbocyclic or heterocyclic ring fused to the specified ring, or an alkyl group with 8 to 18 carbon atoms, _Μ an alkylamido group with 8 to 18 carbon atoms, or an aryl group, e.g. phenyl, naphthyl or Aftylamidoarylgroppe with 8 to 18 carbon atoms in the alkyl part, or more of these hydrophobic groups, whose overall effect in terms of giving it a hydrophobic character is the same as two ABcylamido groups with 3 Ws 12 carbon atoms and two alkylarnktoaryl groups with 3 to 12 carbon atoms in the alkyl part.

It has proven to be particularly advantageous if the group —X —A ¹ —Rj is unable to react with oxidized aromatic color developing agent.

Numerous heterocyclic compounds with a molecular weight of less than 100 (except the Marcapto or selenol group), e.g. the compounds known from GB-PS 11 38 842, were not found as bleach inhibitors, but rather as bleach accelerators.

The use of BIR couplers which are used to release Bleach inhibitors with an acidic thiol or selenol group are capable. The acidity of the thiol or Selenol groups can be influenced by the group be at the. the thiol and selenol groups are bound, e.g. B. by a heterocyclic or carbocyclic ring. Alternatively, others can Groups bring about the acidity of the compound. So gives z. B. a carboxyl group attached to a Carbon atom sits, which is adjacent to the carbon atom bearing the specified groups, z. B. 2-mercaptolauric acid, the desired acidity. Other types of electron withdrawing groups, e.g. B. Nitro groups and halogen atoms can also impart acidity to the thiol and selenol groups.

According to a particularly advantageous embodiment of the invention, the one capable of auxiliary image recording contains Silver halide emulsion layer has a color coupler with a group of the formulas:

(b)

45

50

35 (C)

Il

R - C - N
O

Il

R ² -C N

O ^

R ^: - C - Ni

Hy

N-

S -

(d) R ^J -Z-C

O N-

, H H

(e) RJ-C-N-C

-N

Il

c — s—

C — S—

H N

130262/66

Il

R- '-C -N

H ) "

> - ■ - N

N =

R ² is an alkyl group with 1 - 17 carbon atoms,

R ³ is an alkyl group with 5 to 17 carbon atoms,

Z equals a sulfur atom or the group -NHCO- and

η is 1, 2, 3, 4 or 5.

Preferably, the ^{alkyl groups represented by R 2} and R ^{3 have} 8 to 12 carbon atoms.

Typical bleach inhibitor-releasing couplers which can be used according to the invention are e.g. B .:

1. l-Hydroxy-4- [l- (3-decanamidophenyl) tetrazol-5-ylthio] -N- (2-n-tetradecyloxyphenyl) - 2-naphthamide;

II. 1-Hydroxy-4- (5-decanamido-1,3,4-thiadiazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) - 2-naphthamide;

I11. 1-hydroxy-4- (5-decanamido-1,3-benzimidazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide;

IV. 1-Hydroxy-4- (5-nonanamido-U-benzoxazol-2-ylthio) -2- [4- (2,4-di-tert-amylphenoxy) -n-butyl] naphthamide;

V. l-Hydroxy-4- (5-nonanamido-1,3-benzothiazoI-2-ylthio) -2 - [/ J- (2,4-di-tert-amylphenoxy) -n-butyl] naphthamide; w

VI. a- (PivalyI) - «- (5-nonanamido-1,3,4-triazol-2-yithio) -2-chloro-5- [y- (2,4-di-tert-amyiphenoxy) -butyramido] -acetanilide; VII. 1-Hydroxy-4- (4-nanamidodiacet-3-ylthio) -

N- (2-n-tetradecyloxyphenyl) -2-naphthamide; 4th VIII. 1 - Hydroxy -4- (4-dodecanamido-1,3-pyrimidin-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide;

IX. 1-Hydroxy-4- (1-carboxy-4-decanamidocyclohexylthio) -2- [2-2,4-di-tert-amyIphenoxy) -so

n-butyl] naphthamide;

X.! -Hydroxy-4- {4-dodecsnam! DocydQhexenl-ylthio) -2- {zl- (2,4-di-tert-amylphenoxy) -n -butyl] naphthamide;

XL «- (PivaIyl) -« - (4-nonanamidophenyIthio) -

2-chloro-5 - [} '- {2,4-di-tert-amylphenoxy) butyramido] acetanilide; XII. oc- (pivalyl) - «- (dodecanoic add-2-ylthio) -2-chloro-5- {y- {2,4-di-tert-aniylphenoxy) butyramido] acetanilide; ·

XIIL l-Hydroxy-H4-octyIbenzoylthio) -N- (2-n-te-

tradecyloxyphenyI) -2-naphthamide; XIV. 1-Hydroxy-i-iS-decylthio-1 ^ -thiadiazol-2-ylthk>) - N- (2-n-tetradecyloxyphenyI) -2-naphthamide;

XV. a- (PivalyI) - «- (benzophenonthio) -2-ch] oro-5 - (^ - (2,4-di-tert-aniylphenoxy) butyrainido] acetanOid;

XVI. 1-Hydroxy-4- (5-decylcarbamoyl-1,3-benzimidazol-2-ylthio) -2- [4- (2,4-di-tert-amylphenoxy) -n-butyl] naphthamide; XVII. 1 -hydroxy-4- (6-decyloxy-1,3-benzoxazole- -, 2-ylthio) -N- (2-n-tetradecyloxyphenyl) -

2-naphthamide;

XVIII. «- (Pivalyl) -« - (5-phenoxy-1,3-benzothiazol- ^Χ Ν 2-ylthio) -2-chloro-5- [y- (2,4-di-tert-amyl-

phenoxy) butyramido] acetanilide;

_ ^ κι XIX. l- | 4 - [«- (3-Pentyldecylphenoxy) butyramido] -

phenyl) -3-ethoxy-4- (5-nonanamido-1,3,4-thiadiazol-2-ylthio) -5-pyrazolone; XX. 1-hydroxy-4- [l - (3-decanamidophenyl) tetrazol-5-ylseleno] -N- (2-n-tetradecyloxyphenyl) - 2-naphthamide;

XXI. ! -Hydroxy ^ -iS-octanamido-KS-benzimidazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide;

XXI I. 1-Hydroxy-4- (5-nonamido-1,3-benzimidazol-2-ylthio) -N- (2-n-tetradecyioxyphenyl) -2-naphthamide;

XXIII. l-Hydroxy ^ -iS-undecanamido-l.S-benzimidazoI-2-ylthio) -N- (2-n-tetradecyloxy phenyl) 2-naphthamide;

XXIV. I-Hydroxy 1-S-dodecanamido-1, S-benzimidazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide;

XX V. 1 - (2,4,6-Trichlorophenyl) -3- (3 - [«- (2,4-di-tert.-

amylphenoxy) acetamido] benzamido (-4- [1 - (3-

decanamidophenyl) tetrazol-5-ylthio] -5-pyr-

azolone;
XXVI. «- {3 - [« - (2,4-Di-tert-amylphenoxy) butyr-

amido] benzoyl) - «- [l- (3-nonamidophenyl) -

tetrazol-5-ylthio] -2-methoxyacetanilide; XXVII. l- (2,4,6-trichlorophenyl) -3-pentadecyl-

4-fl- (3-undecanamidophenyl) -tetrazol-5-yl-

thio] -5-pyrazolone;
XXVUI. 4- [1- (3-decanamidophenyl) tetrazol-5-ylthio] -

phenol;
XXIX. 5-methoxy-2- [a- (3-n-pentadecylphenoxy) -

butyramido] -4- [1- (3-octanamidophenyl) tetra-

zol-5-y! thio] phenol;
XXX. 1 - (4 - [«- (2,4-Di-tert-amylphenoxy) butyr-

amido] -phenyl} -3- (l-pyrrolidine) -4- [l- (3-de-

canamidophenyI) tetrazol-5-ylthio] -5-pyr-

azolone;
XXXI. «-Benzoy! -« - [l- (3-decanamidopheny!) - tetra-

zol-5-ythio] acetophenone;

XXXII. 1-phenyl-3-octadecylamino-4- [1- (3-decanamidophenyl) tetrazol-5-ylthio] -5-pyrazolone;

XXXIII. 1-Hydroxy-4- [3-nonamidophenyl] tetrazole-5-vlthiol-3 ', 5'-di-carbomethoxy-2-nephthanilide and

XXXIV. α- (2-Furoyl) - «- [1- (3-dodecanamidophenyl) - tetrazol-5-ylthio] -3 ^ -disulfoacetanilide, dipotassium salt.

According to a particularly advantageous embodiment of the invention, the silver halide emulsion layer capable of auxiliary image recording contains 1-hydroxy-4- (5-nonananiido-13-benamidazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide as the color coupler.

The precursor compounds of bleach inhibitors which can be used according to the invention are known compounds or according to customary known processes, how they z. B. in US-PS 32 27 554 for the production described by thioether couplers can be produced.

The hydroquinones which are suitable for the production of recording materials according to the invention Bleach inhibitor precursors also include naphthoquinones and substituted hydroquinones. The use of so-called BIR hydroquinones has proven to be particularly advantageous, which have a hydrophobic group which is attached to the aromatic nucleus via a sulfur or Seleno bridge is bound. These compounds set in the implementation with oxidized developer connectors κι fertilize an acidic thiol or selenol (cf.e.g. Mees and James, "The Theory of the Photographic Process," McMillan Co., 1966, pp. 278-311).

The use of BIR hydroquinones of the following formula has proven to be particularly advantageous grasslands:

in which X, A ¹ and Ri have the meaning given and in which also mean:

Ra in each case a hydrogen atom or a masking group which can be split off _{in an alkaline medium and R 5, e.g.} B. an acyl group, for example r> an acetyl, mono-, di- or trichloroacetyl, mono-, di- or trifluoroacetyl or a perfluoroacyl (e.g. -butyryl-) group or a pyruvyl, alkoxalyl -, nitrobenzoyl or cyanobenzoyl group and

R ₆ , R7 each represent a hydrogen atom or an optionally _{substituted and R 8} alkyl group of the meaning given for Ri, or

Re working together to complete a and R7 fused-on benzene ring required -r, Atoms.

The use of the following BIR hydroquinones has proven to be particularly advantageous:

23-dimethyl-5- {1- (3-nonanamidophenyl) tetrazol-5-ylthioJtydroquinone; 23-Dimethyl-5- {5-decanamido-1,3,4-thiadiazoi-2-ylthio) hydroquinone:

3-ButyI-5 <5-decanamido-13-benzimidazolyl-2-jithio) hydroquinone;

S-Oct ^ -S ^ S-nonananiido-1 ^ -benzothiazol-2-yhhk>) hydroquinone;

23-Dmetbjrt-5- (1-carboxy-4-decananiidocyclohexyithio) hydroquinone;

23-diethyl-5- (4-dodecanamidocyclohexen-1-ylthk>) hydroquinone and 23-diethyl-5- [1- (3-decanamidophenyl) tetrazol-5-ykeleno-hydroquinone.

Such BIR hydroquinones are chemically related to the thiosubstituted development inhibitors of the type described in US Pat. No. 3,36,022 and can be prepared by processes as described in the patent.
Further precursor compounds of silver bleach inhibitors which can be used according to the invention are, for. B. from GB-PS 12 24 555 and BE-PS 7 13 448 known, the —S — Y group of the structural formula listed on page 2 of the given GB-PS by the group -X- (A ¹ J- Ri is replaced.

Usually, bleach baths are more powerful oxidizing agents as bleach-fix baths. It has therefore proven to be particularly advantageous if the during the Color development bleach inhibitors formed are comparatively less hydrophilic when the scene image recording silver to graze oxidized with a bleach bath. In this case z. B. Bleach Inhibitors usable, which by a comparatively hydrophobic group, z. B. a long chain fatty acid group substituted are.

The starting from the recording materials according to Scenes that can be produced according to the invention can optionally also be of neutral density. Such Images can be prepared from a coupler or a mixture of couplers which produce dyes or dye combinations react which provide a neutral density. Just like with color images the silver of the scene recordings will also carry through when producing neutral density images Bleach and fix removed.

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

F i g. I the exposure and processing of a photographic recording material according to the invention in the scheme, and

F i g. Fig. 2 is a plan view of a photographic recording material according to the invention in the scheme.

The in Fig. 1 recording material, shown schematically in section, consists of a transparent support 22 on which are arranged: a blue-sensitive gelatin-silver halide emulsion layer 23 capable of generating yellow dyes, a red-sensitive gelatin-silver halide emulsion layer 24 capable of generating cyan dyes, a green-sensitive gelatin silver halide emulsion layer 24 capable of generating Gelatin-silver halide emulsion layer 25 capable of purple dyes and a blue-green-sensitive gelatin-silver halide emulsion layer 26 capable of generating cyan dyes, intended for recording images and containing a precursor compound for a bleach inhibitor. The auxiliary layer 26 is sensitized in such a way that its sensitivity peak is approximately 480 nm. The photographic sensitivity of the layer 26 is about 0.4 og E less than that of the less sensitive layer of the two layers 23 (blauemnfindlich) and 25 (green-sensitive) when at 480 nm expose! Is. To simplify the illustration, the usual known adhesive, intermediate and cover layers have been omitted from the drawing.

Stage 1 shows the exposure of the recording material through the original consisting of a negative, for the sake of simplicity, in the form of a single image layer 21 on the transparent layer support 20 The exposure for the scene image recording is done with white light and the exposure for soundtrack recording with blue-green light, the maximum intensity of which is around 480 nm and whose bandwidth is about 20 nm at half the height. In practice, it can be the one used for exposure Original around a multi-layer, multi-colored Recording material or a scene seen through a camera lens. Also located

In practice, the recording of the scene and the soundtrack are usually on separate templates, whereby these originals are photographed separately shortly after each other

Step 2 shows the state of the exposed recording material after the development of the latent image by means of a color developing agent. Layers 23a, 24a, and 25a are included in the scene design districts 210 silver and dye brothers. The districts 29 of these layers were not moistened, so that in these Districts also no latent image was generated. Silver halide is therefore present in districts 29. the Layer 26a for auxiliary image recording was chosen because of its particular photographic sensitivity and spectral sensitization is not exposed and therefore contains in both districts 29 and 210 silver halide. Layers 23a, 25a and 26a received due to their particular photographic sensitivity and spectral sensitization Soundtrack exposure and contain silver and dye images in soundtrack districts 27, as well as silver halide in the soundtrack districts 28.

In the case of FIG. 1, there is the bleach inhibitor produced in layer 26a from a moderately diffusible compound, which developed not only from that in region 27 of layer 26a Silver is adsorbed, but also diffused into the layer 25a of the districts 27 and from the silver present there is adsorbed. The layer 24a with no soundtrack exposure has both the soundtrack areas 27 as well as 28 silver halide.

Step 3 shows the state of the recording material after it was brought into contact with a bleach-fix bath and then washed with water. In the image areas 29, the layers 23b, 24b and 25b are now transparent, since the silver halide present there has been fixed. The scene areas 210 of these layers contain dyes since the developed silver present there has been removed by bleaching and fusing. The auxiliary layer 26b is in

Table I A

the scene areas 29 and 210 also transparent, since the silver halide present there has been fixed. In the soundtrack areas 28, all four layers are transparent because the remaining silver halide has been fixed. Layer 23b and the lower part of layer 256 contain dye in soundtrack areas 27 because the developed silver present in these layers was removed by bleaching and fusing because it was not protected by the bleach inhibitor formed during color development. Layer 26b and the upper part of layer 25b contain silver and dye in the soundtrack areas 27, since the silver present there was protected by the bleach inhibitor formed during color development.

The developed recording material thus has a high quality color scene record and a silver soundtrack recording, the silver soundtrack recording simply without Use of a special treatment bath for producing the soundtrack is obtained.

In Fig. A typical motion picture film with sound track areas 11 is shown schematically in FIG. The ones in the production design districts Image fields shown in 12 contain the individual scene image recordings. The perforation 13 is used to transport the motion picture film.

The following examples are intended to explain the invention in more detail.

at

ιs pi e1

Strips of photographic recording materials made of a transparent cellulose acetate layer support with a gelatin-silver halide emulsion layer applied thereon with a ratio of chloride to bromide of 80:20, an average grain size of the silver halide of 0.1 micron and 2.15 g of gelatin per m ^{2 of support area} as well as those in the Couplers listed in Table IB were exposed through a step wedge and then processed as indicated in Table IA below

Procedure No. 1 2

Treatment temperature 38 ° C 24 ° C

3
26.5 ° C

1. Color development 90 sec. 2. Breaker fixer 40 sec. treatment 3. Water 60 sec. 4th Bleach-fix 40 sec. 5. Water 80 sec. 6th Stabilize 10 sec.

9 min.
2 min.

2 min.

2 min.

6 min.

10 sec.

5 min. 20 sec.
2 min.

2 min.

1 min. 30seIc.

6 min.
10 sec.

The treatment baths used had the following composition:

1. Color developer

Sodium hexametaphosphate 2 g

Sodium sulfite, anhydrous 4 g

2-amino-5-diethylaminotoluene 3 g

monohydrochloride

Sodium carbonate, monohydrate 20 g

Potassium bromide 2 g

made up to 1 liter with water

(pH 10.65)

2. Interrupt fixer

Sodium thiosulfate

Nairium sulfite, anhydrous

Acetic acid, 28%

Boric acid, crystals

Potassium alum

filled up with water

\. Bleach-fix bath

Ethylenediaminetetraacetic acid,

Natrii: m-iron salt
Natnumsulfii

240 g
15 g

48 ml
75 g

15 g
1 liter

60g 12 g

3S

Ammonium thiosulfate, 60%

Ethylenediaminetetraacetic acid solution,

Tetrasodium salt ammonium thiocyanate made up with water.

5. Formaldehyde stabilization bath (37% by weight solution) Octylphenoxypolyäthoxyäthano! topped up with water

Table 1 B.

200 ml 6.7 g

12 g 1 liter (pH 6.8)

20 ml 2 ml 1 liter 10

There were further comparative tests to determine the percentage of silver that was obtained remains carried out if process steps 4 (bleach-fix) and 5 (washing) are omitted. The on Comparative samples obtained in this way contained only developed silver as the remaining silver halide was fixed out.

The silver density measurements were made with a densitometer at 900 in the results obtained are compiled in Table 1B below

Recording material

Bleach inhibitor precursor (BIR coupler) type mg / m ²

Competing coupler silver as a method

Silver halide no.

Type mg / m ²

mg / m ²

ABBBBCCCCCDDEEF Remaining
silver
in %

140 G 807 666 I (38) 100 129 G 807 807: 2 (24) 100 129 G 807 807 * (26.5) 100 129 G 807 807 100 129 H 1150 786 100 129 G 807 786 100 129 J 807 753 100 129 K 1045 721 100 129 H 1150 721 100 129 L. 807 743 100 129 K. 1045 721 100 129 L. 807 786 100 140 G 807 721 100 140 H 1150 721 100 323 G 807 786 100

Chemical constitution of the couplers used: 1) BIR couplers:

A. 1-Hydroxy ^ -fl-p-undecanamidophenyO-teirazol-5-ylthio] -N- (2-n-tetradecyloxyphenyI) -2-naphthamide;

B. 1-Hydroxy-4- (5-nonanamido-1,3,4-thiadiazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide;

C. 1-Hydroxy-4- (5-nonanamido-1,3-benzimidazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide;

D. 1-Hydroxy-4- (5-nonanamido-1,3,4-thiadiazol-2-ylthio) -2- [d- (2,4-di-tert-amylphenoxy) -n-butyl] naphthamide ;

E. 1 -hydroxy-4- [5- {3,5,5-trimethylhexanamido) · 1,3,4-thiadiazol-2-yithio] -N- (2-n-tetradecoxyphenyl) -2-naphthamide;

F. "- (Pi vaiyl) -a- (5-nonanamido-1,3,4-thiadiazol-2-ylthio) -2-chloro-5 - [}> - (2,4-di-tert-arnylphenoxy ) -butyramidoj-acetanilide.

2) Competing Couplers:

G. l-Hydroxy-N- (2-n-tetradecyloxyphenyl) -2-naphth-

amide;
H. 1 - (2,4,6-Trichlorophenyl) -3-) 3- [y- (2,4-di-tert-amyl-

phenoxy) acetamido] benzamido} -5-pyrazolone; J. 1 -hydroxy-2- {d- (2.4-di-tert-amylphenoxy) -

n-butyl] naphthamide; K. l- (6-chloro-2,4-dimethylphenyl) -3- [a- (m-penta-

decylphenoxy) butyramido] · 5-pyrazolone; L 1 - (2,4,6-trichlorophenyl) -3-pentadecyI-5-pyrazolone.

The received. Results show that during the development process a sufficient amount of Bleach inhibitor was imagewise released to all silver developed during the soundtrack areas to retain the bleach-fixation of the recording material.

Multilayer color photographic recording materials have become with three more sensitive, 5 intended for the recording of scenes, color-forming Gelatin-silver halide emulsion units and those described, intended for auxiliary image recording Gelatin-silver halide emulsion layers prepared. The recording materials obtained were then exposed through a colored original without exposing the auxiliary layer, and a soundtrack recording exposed. The recording materials were then processed as indicated. It Color scene recordings made from dyes practically free of silver became excellent as well Silver soundtrack recordings preserved.

Example 2

Strips of single layer photographic material of the type designated as recording material No. 2 in Example 1 were carried out by exposed a wedge, whereupon, as in the following Table II indicated, were processed at 38 ° C. The numbers given in Table 11 represent seconds.

Table II

1. Pre-bath treatment

2. Soak

3. Color development

4. Watering

5. Interrupt bath treatment

6. Breaker fixer treatment

7. Soak

8. Bleach-fix

9. Soak

! 0. Stabilize
Remaining silver density

The chemical composition of treatment baths 3, 6 and 9 was the same as that of the treatment baths 1, 2 and 6 of Example 1. The chemical composition of the others used Baths was as follows:

1. Pre-bath

Procedure No. 10 2 10 3 10 4th 10 5 10 1 10 10 10 10 10 90 90 90 90 90 10 10 10 10 10 - - - 60 - 60 60 60 - - 30th 30th 30th _ - 60 90 60 60 120 120 120 120 120 10 10 10 10 10 100% 100% 88% 710/0

Borax 20 g

Sodium sulfate, anhydrous 100 g

Sodium hydroxide, 10% solution 10 ml made up to 1 liter with water

pH 9.3

5. Interrupt bath

Glacial acetic acid 24.5 ml

Sodium bisulfite 6.5 g

made up to 1 liter with water

pH 3.76

8. Bleach-fix bath (always used except for procedure no.3)

Hydrochloric acid 9.2 ml

Sodium sulfite 12 g

Ammonium-iron-ethylenediamine- 92 ml

tetraacetic acid (1.56 molar solution)

Ammonium thiosulphate (60% solution) 200 ml

made up to 1 liter with water

pH 6.5

8. Bleach-Fix Bath (Procedure No. 3)

Ethylenediaminetetraacetic acid, 60 g

Sodium iron salt

Ethylenediaminetetraacetic acid, 7 g

Tetrasodium salt

Sodium sulfite 20 g

Ammonium thiosulfate 200 ml

(60% solution)

Potassium iodide 4 g

made up to 1 liter with water

pH 6.8

The recording material processed according to Procedure No. 1 was fixed but not bleach-fixed. Because this recording material is not bleached it contained 100% of the developed silver and was used as a reference value for determining the effectiveness of the bleach inhibitor. The percentage of silver retained was determined according to that described in Example 1 Procedure determined.

The results obtained show that the silver density retained was so great as to be qualitative in all cases high-quality silver-tone traces have been preserved.

Became the gelatin-silver halide emulsion layer used as an auxiliary layer on a multi-layer

J _{1 was} applied to color photographic recording material with three more highly sensitive, color-forming gelatine-silver halide emulsion units capable of recording scenes, and the recording material obtained was replaced by a colored original

jo exposed a soundtrack recording without exposing the auxiliary layer exposed and then according to one of the specified procedures No. 2 to 5 processed, so color scene image recordings, which consisted of dye and were practically free from

Ji were silver, as well as excellent soundtrack recording Obtained from silver.

Example 3

Three multi-layer color photos were tested

4 (1 graphic recording materials with scene image recording and soundtrack recording areas, each of which has three capable of scene image recording had color-forming units. Each unit was across from a different primary color range

4> of the visible spectrum sensitive. The recording materials also contained an auxiliary layer capable of recording audio tracks, as indicated below Composition sensitive to the blue region of the visible spectrum.

•> o The recording materials to be tested were exposed to white light through color image negatives, as well as a soundtrack negative through one Filter pack, which is a narrow band of light with a peak at 470 nm and a bandwidth of 20 nm

5Ί exposed at half permeability, whereupon the exposed recording materials were processed according to procedure no. The recording materials used had the structure given below. The in clap

Numerical values in bo mers relate to mg / m ² .

Recording material I

The following layers were applied in the following rows to one side of a transparent cellulose acetate layer carrier:
(1) A blue-sensitive, scene-recording capable, color-forming photographic unit

from gelatine (3650), silver (645) in the form of SiI-berbromidjodid, with 1% iodide, a diffusion-resistant, capable of forming a yellow dye, open-chain ketomethylene cup! sr (1400) and Dibutyl phthalate as a coupler solvent (1400),

(2) an intermediate layer of gelatin (645) and 23-dioctylhydroquinone (81),

(3) a red-sensitive, color-forming photographic unit capable of recording scenes, made of gelatine (3000), silver (430) in fenn of silicon chloride bromide with 20% bromide, a diffusion-resistant phenolic photographic coupler (810) capable of forming a cyan dye and dibutyl phthalate as coupler solvent (2420),

(4) an intermediate layer of gelatin (645) and 23-dioctylhydroquinone (81),

(51 a green-sensitive, color-forming photographic unit, capable of recording scenes, made of gelatine (2360), silver (860) in the form of silver chlorobromide with 20% bromide, a diffusion-resistant photographic 5-pyrazolone coupler capable of forming a purple dye (1450) and tricresyl phosphate (700 ) as a coupler solvent,

(6) an intermediate layer of gelatin (645) and 23-dioctylhydroquinone (81),

(7) an auxiliary layer made of gelatine (1600), silver (750) in the form of silver chloride bromide ... with 20% bromide, with an average grain size of about 0.1 micron, BIR, capable of sound track recording, which is sensitive to the blue region of the visible spectrum -Coupler A of Example 1 (140), Coupler G of Example 1 (810), 2 ^ -dioctylhydroquinone (81) and tricresyl phosphate (485) as coupler solvents, as well as

(8) a top layer of gelatin (970).

Recording material II

On one side of a transparent cellulose acetate support the following layers were applied in the following order:

(1) A blue-sensitive, still-picture capable, color-forming photographic unit made of gelatine (3650), silver (645) in the form of silicon bromide iodide with 1% iodide, a diffusion-resistant, photographic open-chain ketomethylene couplers capable of forming a yellow dye (1400) and dibutyl phthalate (1400) as coupler solvents,

(2) an intermediate layer of gelatin (645) and 23-dioctylhydroquinone (81),

(3) a red-sensitive, color-forming photographic unit capable of recording scenes, made of gelatine (3000), silver (430) in the form of silver chlorobromide with 20% bromide, a diffusion-resistant, photographic phenolic coupler capable of forming a cyan dye (810) and dibutyl phthalate (2420) as a coupler solvent,

(4) an auxiliary layer of gelatin (1600), silver (750) in the form of silver chlorobromide with 20% bromide with an average grain size of about 0.1 micron, the BIR coupler A des Example 1 (140), Coupler C of Example 1 (810), 2,5-dioctylhydroquinone (81) and tricresyl phosphate (485) as coupler solvents,

(5) a green-sensitive, for scene picture recording capable color-forming photographic unit made of gelatine (2360), silver (860) in the form of

Silver chloride bromide with 20% bromide, a diffusion-resistant, 5-pyazolone photographic couplers capable of forming a magenta dye (1450) and tricresyl phosphate (700) as coupler ίο solvent, as well

(6) a top layer of gelatin (970).

Recording material III

ι =, On one side of a transparent cellulose acetate layer support, the following layers were applied in the following order:

(1) a blue-sensitive, color-forming photographic input capable of recording scenes

2 »is made of gelatine (3650), silver (645) in the form of

Silver bromide iodide with 1% iodide, a diffusion-resistant, capable of forming a yellow dye photographic open chain ketomethylene couplers (1400) and dibutyl phthalate (1400) as

2 -, coupler solvent,

(2) an intermediate layer of gelatin (645) and 2,5-dioctylhydroquinone (81),

(3) a soundtrack capable of recording opposite the blue part of the visible spectrum

in a sensitive auxiliary layer of gelatine (1600), silver (750) in the form of silver chlorobromide with 20% bromide with an average grain size of about 0.1 micron, BIR Coupler A of Example 1 (140), Coupler G of Example

j-, 1 (810) 2,5-dioctylhydroquinone (81) and tricresyl phosphate (485) as a coupler solvent,

(4) a red-sensitive, color-forming photographic unit, capable of recording scenes, of gelatine (3000), silver (430) in the form of silicon chloride bromide with 20% bromide, a diffusion-resistant phenolic coupler (810) capable of forming a cyan dye and dibutyl phthalate (2420) as a coupler solvent,
. (· -, (5) an intermediate layer of gelatin (645) and 2,5-dioctylhydroquinone (81),

(6) a green-sensitive, color-forming photographic unit capable of recording scenes, made of gelatine (2360), silver (860) in the form of silver chlorobromide with 20% bromide, a diffusion-resistant photographic 5-pyrazolone coupler (1450) capable of forming a purple dye and tricresyl phosphate ( 700) as a coupler solvent, as well as
(7) a top layer of gelatin (970).

The developed recording materials contained yellow, purple and cyan color image records, which were practically free of silver, as well as excellent silver-tone track recordingsep.

^{b <)} B eis ρ ie 1 4

Strips of photographic recording materials, consisting of a transparent cellulose acetate support and a coated thereon e5 layer of a fogged, direct positive gelatin-silver halide emulsion of the type known from FR-PS 20 821 with a content of the BIR-

Couplers, and competing couplers, were exposed through a step wedge and thereby, as in the Table IV-A given below, processed.

Table IV-A

1. Schwarzwi development

2. Interrupt bath

3. Soak

4. Reverse flash exposure

5. Color development

6. Soak

7. Bleach-fix

8. Soak

9. Stabilize
Treatment temperature

30 sec. 30 sec.

1 min.

4 min.

1 min.

1 min.

1 min. 10 sec. 52 ° C

The composition of the treatment baths used was as follows:

1. Black and white developer

H ₂ SO ₄ 1.8 ml

Sodium sulfite 25 g

1-phenyl-3-pyrazolidone 0.6 g

K ₂ CO, 16.0 g

Hydroquinone 8.0 g

NaBr 1.5 g

NaHCOi 12.0 g

KI 7 mg

Diethylene glycol 12.0 ml

made up to 1 liter with water

pH 9.9

2. Interrupt bath

Water 800 ml

Glacial acetic acid 27 ml

NaHSO ₃ 8.7 g

made up to 1 liter with water

5. Color developer

Sodium sulfite 2.5 g 4-Amino-3-methyl- (N-ethyl-N-meth- 14.0 g oxyethyl) aniline-1,5-naphthalene. Di- sulfonic acid K, COi 36.0 g NaBr 03 g K) 0.028 g Citrazinic acid 1.0 g KOH (45% solution) 3.0 ml j.b-dithiaoctane-1,8-thiol 1.0 g topped up with water 1 uter PH value 10.7 calibration fixer
Sodium Iron Ethylenediamine Tetra 60.0 g acetic acid Sodium sulfite 12.0 g Ammonium thiocyanate 12.0 g

Ammonium thiosulfate (60% solution) 200 ml of tetrasodium ethylenediamine tetra- 6.7 g

acetic acid

made up to 1 liter with water

pH 6.68

9. Stabilization bath

Formaldehyde (37% strength by weight solution) 20 ml octylphenoxy-polyethoxyethanol 2 ml

made up to 1 Liier with water

The composition of the records used The following table IV-B shows the materials used.

Table IV-B

Aiif7eichmingv gelatin
material

BIR coupler

No.

mg / m-

mg / m ² compet.
Coupler

mg / m ²

Silver as silver halide

mg / m ²

2150
2150
2150

O A C

323 269

The composition of couplers A, C and G results from Example 1.

The silver densities obtained were measured at 90 nm using a densitometer. The received Results are shown in Table IV-C below.

Table IV-C

On-silver density

drawn- developed restrained

potential

material Min. EP >> Max. EM Min. EM Max.) No.

1 2 3

W min. tion.

i, 40

1.42 138

036 036 1.02

0.05 0.05 0.04

0.06 G
G
C-

806
806
806

763 763 850

034 The results show that a sufficient amount of bleach inhibitor is imagewise released during development to hold back a substantial portion of the developed silver during the process. The retained during the bleach-fixing silver presented a negative image represents and keir normal positive image that will then passworder would be had there been in the auxiliary layer negative, ansentwickel bares silver and the ups

ZCWrI lrciif | fe ^ ifrfrflq it ^ ml in cntSPTCCnCtHlCT WCBC UliiKCflf '

has been developed wire, like the specified photo graphic recording materials.

The gelatin silver halide emulsion layers described above were used as auxiliary layers on multilayer color photographic color-forming layers with three more highly effective color-forming layers that are known to be capable of setting the scene

E-MmnnumbeSchtung; Max. E = Maimnnnnbelich- The snares were arranged and sensed in such a way that each of them is pri-

mars color range of the visible spectrum was sensitive. In the auxiliary layer was due to their special Radiation sensitivity in imagewise exposure of the scene image recording units no image generated. The recording materials were exposed through a colored original without the Auxiliary layer was exposed and exposed to a soundtrack recording. Thereupon the exposed Recording materials as indicated in Table IV-A processed. Color image recordings were obtained which were virtually silver free, as well as excellent silver negative soundtrack recordings.

Example 5

A multilayer color photographic recording material, the structure of which corresponded to that of recording material I of Example 3, with the exception that the auxiliary layer no average grain size of about 0.1 micron, the BIR coupler l-hydroxy-4- [l- (3undecanamidophenyl) -tetrazol-5-ylthio] -N- (2-n-tetradecyloxyphenyl) -2-naphthamide (160), the competing coupler 1 hydroxy-N- (2-n-tetradecyloxyphenyl) -2-naphthamide (810), tricresyl phosphate (485) as a coupler solvent and the sensitizing dye 3-ethyl-5- (3-ethyl-2-benzothiazolinylidene) rhodanine
3-Ethyl-5- (3-ethyl-2-benzothiazolinylidene) -thodanim (150 mg / mol silver), which caused a maximum sensitization at about 480 nm, passed through a step wedge with white light and a sound track with light a narrow bandwidth, the maximum intensity of which was 470 nm, whereupon the exposed recording material was processed as follows:

Sec.

1. Pre-bath treatment 10

2. Soak 10

3. Color development 90

4. Soak 10

5. Breaker fixing bath treatment 60

6. Soaking 30

7. Bleach-fix 60

8. Soak 120

9. Stabilize i0
Treatment temperature 38'C

Treatment baths 3.5 and 9 had the same composition like baths 1. 2 or 6 of the example i. The pre-bath used had the same composition like that used in Example 2, and the bleach-fix bath used had the same composition such as the bath used to carry out Procedures 2, 4 and 5 of Example 2. The modulation density of the recording material obtained was within the range which corresponds to a usable sound volume and good recording material durability.

The recording material written on was exposed through a multicolored original and a sound track and then developed as indicated, the image and soundtrack recordings became excellent obtain.

Example 6

To prepare a comparative material, a gelatin silver chlorobromide emulsion, the halide component of which consisted of 80 mol% chloride, was applied to a cellulose triacetate layer support in such a way that about 2.15 g of silver and about 4.3 g of gelatin were used ^{per m 2 of support surface.} The layer further contained per m ² of support surface 0.86 g of the competing coupler 1-hydroxy-2 - [/ d- (2,4-di-tert-amylphenoxy) -n-butyl] naphthoamide, dissolved in 13g / m ^J of the coupler solvent, di-n-butyl phthalate.

Correspondingly, a further recording material was produced, except that the layer g additional per m ^{2 of} support surface 0.43 of a bleach inhibitor-releasing hydroquinone compound 2,3-dimethyl-5- [l - (3-nonanamidophenyl) -tetrazolyI- 5-ylthio] hydroquinone were added.

Sections of the two recording materials were exposed and processed as described in Example 1. The results obtained showed that in the material containing the hydroquinone compound after Bleach-fixing had retained a sufficient amount of silver to provide a usable soundtrack, whereas no silver was retained in the comparative material.

Corresponding results were obtained when the specified procedure was repeated, but replacing the color developing agent used by a black and white developing agent of Example 4 type described.

Correspondingly advantageous results as described in Example 3 were also obtained when the there was repeated obtained when the BIR coupler A used of the specified recording materials 1, II and III. by the one in this example BIR hydroquinone compound used was replaced.

For this purpose 1 sheet of drawing

130262/66

Claims (4)

Patent claims: 1. Color photographic recording material from a - optionally transparent - layer support, at least one for recording scene images capable color-forming silver halide emulsion layer, one capable of auxiliary image recording, preferably soundtrack recording - possibly a sensitizing color ι ο substance-containing - silver halide emulsion layer, and optionally intermediate and / or Cover layers, characterized in that the silver halide emulsion layer capable of auxiliary image recording a) has such a sensitivity that with image-wise Exposure of the silver halide emulsion layer (s) capable of recording scenes in her ksin image is generated that she b) contains a diffusion-resistant precursor compound of a silver bleach inhibitor, which in the presence an oxidized developer compound releases a bleach inhibitor that contains a thiol or contains a selenol group and a hydrophobic group, and optionally c) that it contains an additional compound which μ with a group consisting of an oxidized aromatic primary amine color developer compound can react operate at a color development. 2. Recording material according to claim 1, characterized in that the for auxiliary image recording r> Drawing capable silver halide emulsion layer as a precursor compound a hydroquinone or contains a color coupler which is in the presence of an oxidized developing agent releases a silver bleach inhibitor. 4 » 3. Recording material according to claim 2, characterized in that the silver halide emulsion layer capable of auxiliary building recording contains a color coupler which, in the coupling position, contains a group of the formula —X — A ¹ —Rj -r, in which X is a sulfur or selenium atom,
A ¹ equals a carbonyl group, thiocarbonyl group, carboxymethylene group, a 3-6-membered carbocyclic ring with two free n bonds or a 3-membered heterocyclic ring with at least one carbon atom, one nitrogen, oxygen, sulfur or selenium atom and two free ones Ties, ■ - » R ¹ equals a halogen atom, a nitro group, an optionally substituted alkyl group, an optionally substituted aryl group, an alkylthio group, a carboxyalkylthio group, an arylthio group, an alkylcarbonylalkylthio group, an alkylcarbonylarylthio group, an arylcarbonylarylthio group, in which the specified arylcarbonylalkylthio group Contain 3-22 carbon atoms, an amide group with 4-22 carbon atoms, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxy group or an aryloxy group and a is 0, 1, 2, 3 , 4, 5 or 6, with the proviso that R> does not denote an alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group or amide group with 4-22 carbon atoms, when A ¹ denotes a carbonyl or thiocarbonyl group, the group —A ¹ - R] a molecule r weight of 125-1000, and where a hydrophobic, diffusion-making group ^{is bonded to A 1} , if A ^{1 is} a 3-6-membered, carbocyclic ring with two bonds or a 3-6-membered heterocyclic ring with at least one carbon atom, at least two nitrogen- , Means oxygen, sulfur or selenium atom and two free bonds. 4. Recording material according to claim 3, characterized in that the auxiliary image recording capable silver halide emulsion layer a color coupler with a group of Formulas -N <x R ² - C - N
II R - C - N
U N- (d) R ¹ -Z-C -CYV- VA. -N Il c — s— ic) R '- O N- C - N - C Il -N C-S- N Il in the auxiliary image, the silver developed compared to bleaching is bleached and - possibly at the same time - Is fixed, characterized in that a recording material according to claim 1 is used will. (0