DE2163576A1 - A photographic process for producing scene images and silver tone track type auxiliary images and a photographic recording material for carrying out the process - Google Patents

Description

1163576

Photographic process for producing scene images and silver tone track type auxiliary images and photographic recording material for Implementation of the procedure

The invention relates to a photographic method of manufacture of scene images and silver-tone track type auxiliary images in one and the same recording material, in which, a photographic Recording material consisting of a layer support, at least one applied to it, for Color-forming photographic recordings capable of scene recording Unit with at least one silver halide emulsion layer as well as, if necessary, intermediate and / or top layers exposed, developed into silver-containing scenes and auxiliary images and, after protection of the silver developed in the silver auxiliary picture district against fading, for the removal of picture silver and remaining silver halide is bleached and fixed. ·

The invention also relates to a photographic recording material to carry out the method, consisting of a layer support, three applied to it, for the scene image color-forming photographic units capable of drawing, each with at least one silver halide emulsion layer, which are arranged and sensitized in such a way that each unit is practically primary in relation to another Color range of the visible spectrum sensitive and for recording practically blue, green or red light is capable, as well as, if necessary, intermediate and / or top layers.

Color photographic recording materials with auxiliary images made of metallic silver are known. Reference is z. B. on French patent specification 912 605. For example, B. Color cinema films with traces of silver tone have been known for a long time. The color pictures are usually produced according to the so-called three-color system of photography. According to this system, color images are formed from three eubtractive dyes: a yellow dye to control blue light, a magenta dye to control green light, and a cyan dye to control red light. These dye images can be produced by various methods.

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So can ζ. B. color images are produced according to the so-called. Color bleaching process. To carry out this procedure, a film is used, which is in three separate layers, one of which each is sensitized to a primary color range of the visible spectrum, each a preformed subtractive one Dye is incorporated therein which is destructible depending on that in developing a latent photographic Image produced silver.

* According to another known method of making a Three-color recording using the subtractive color method in a photographic recording material that has three on top of each other arranged silver halide photographic layers each of which is virtually sensitive to a primary color region of the visible spectrum, in the photographic Ways recorded a picture. Such photographic silver halide layers can be photographic color couplers contain the subtractive dyes when coupling with oxidized developer compounds of the primary aromatic amine type form, the color of which is practically complementary to the primary color areas of the visible spectrum. Optional can use these silver halide photographic layers be free of photographic color couplers. In this case, the color image is developed in a coupler developing composition generated with the formation of non-diffusible subtractive dyes. Following the formation of the dye image, the developed silver and the remaining silver halide must be removed from the image district. This is usually done by bleaching and fixing or bleach-fixing (where it is a one-step bleaching and fixing).

Motion picture optical soundtracks are copied onto the same film on which the scene image was copied. With the optical tone tracks it can be of the type of different density or different districts. The soundtrack can eelbet

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from dyes, from dyes plus silver, from silver compounds, consist of silver plus other metals or of silver alone. The photocell as used in movie projectors used almost exclusively to capture the light passing through an optical soundtrack is on most sensitive to electromagnetic radiation with a wavelength of more than 700 nm with a peak sensitivity of about 800 nm. The subtractive dyes forming the scene have a maximum absorption in the range of 4-00 to 700 nm. As a result, these dyes are almost transparent to infrared radiation and have only a very low modulation effect on that radiation which the photocell is most sensitive.

The chemical reduction of a latent silver halide image formed silver is uniformly opaque to the full spectrum of radiation, which differs from the ultraviolet extends beyond the visible into the infrared, and acts as an excellent modulator for infrared radiation, to which the currently used photoelectric cells are most sensitive. Silver compounds, e.g. B. Silver sulfide and silver tinted with metals, e.g. gold, are also more opaque to infrared radiation than image dyes. From this it follows that optical sound recordings in color cinema films are preferably not made from image colorants, but should consist of substances of other types. Against the presence of subtractive dyes in addition to others However, there is nothing wrong with substances of the specified type.

As already mentioned, the developed silver and the existing silver halide from the set design district must be one Color cinema films are removed after the color image has been produced. At the same time, however, must be developed silver or a silver compound present in the soundtrack area can be kept unchanged if it is the color cinema film

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do such with a sound track of the specified preferred Type. Numerous techniques have been developed around the silver in the soundtrack area of color cinema films during the bleaching and fixing of the silver and residual silver halides to maintain in the production design district. So z. B. the soundtrack district following the formation of the scene and soundtrack images and covered with a varnish prior to removing the silver and silver halide. The varnish prevents that Diffusion of the bleach solution into the soundtrack area. After re-halogenation The lacquer is removed from the silver in the scenery area with the help of a suitable solvent and silver halide is removed from the entire film (see U.S. Patents 1,973,463 and 2,113,329).

Another method currently used to preserve the metallic silver in the audio track district is to and soundtrack images in the silver halide photographic recording material and developing the latent image obtained into metallic silver. In print films, the remaining silver halide is removed by fixing the removed from the entire film. In reversal films only the soundtrack area is fixed with subsequent color reversal development. At this stage, both types of film have a metallic silver soundtrack that is free of residual silver halide is. The metallic silver is then made fixable by bleaching both the soundtrack and scene image areas Silver salt transferred. In the audio track area, the silver salt is converted back into metallic silver by applying a viscous, highly active developer, e.g. B. with the help of usual known strip treatment methods. Then the silver salt present in the scene design area is removed by fixing .

Another known method of preventing the removal of the silver tone trail is to use the silver metal

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a solution that creates a golden hue. The resulting gold-tinted silver metal is bleached and Fixing not removed (see, for example, US Pat. No. 2,263,09).

Another known such method is the The film's soundtrack area is striped with a guaternary To treat ammonium salt, which makes the silver metal unbleachable (see, for example, US Pat. No. 3,243,295). Disadvantages of this, as well as of the specified process, in which a viscous developer solution is applied in strips Sound track district is applied, is that expensive special devices, such. B. a so-called "strip treatment wheel", are required, and it is also disadvantageous that this is known from the stated U.S. Patent Solarift 3,243,295 The process is only useful for the reverse development of color films of the type which, dispersed in a coupler solvent, Couplers are incorporated, and there is also the fact that the quaternary ammonium compounds known from this patent specification only comparatively weakly effective sincL

Another well-known method of preserving the silver metal in the Tonepur district consists in producing a multilayer photographic material which is used during the chromogenic development in the upper layer forms a dye which can be reduced to a leuco dye, which is able to reduce silver ions in solution to silver metal. The developed Tonepur district becomes strip-shaped with Treated water and replaced by a sulfur dioxide gas atmosphere conducted, whereby the gas is absorbed only in the moistened soundtrack area. The absorbed gas reduces the dye to a leuco dye. The film is then passed through an ammonia silver nitrate solution, the leuco dye Silver ions are reduced to silver metal which is deposited in the film (e.g., to U.S. Patent No. 2,286,747).

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It is. also known, the silver located in the soundtrack district to convert into compounds or complexes that the Resist bleaching of silver. So z. B. silver or silver halide converted into silver sulfide before bleaching will. The sulphide is not converted into a fixable silver salt by bleaching and thus remains after the Fixing obtained as silver sulfide (see, for example, US Pat. No. 2,143,787). The treatment solution used can contain both sulphiding and iodising compounds which also convert the silver into a compound that does not remove during bleaching and fixing (see, e.g., U.S. Patent 2,258,976). .

Another known method of making a sound track is to put a separate layer on the back to apply the layer support. Each of the two sides of the film is then treated without the other side being treated with the Bring treatment solutions into contact, for example by flotation of the film on the surface of the solution (referenced be z. U.S. Patent 2,235,033).

The specified procedures are only a part of the patented or known methods or improvements for the production of silver or silver complex soundtracks in color cinema films.

However, all of these presently known methods are numerous Disadvantages, e.g. B., as already mentioned, the requirement to view only part of the film at least once during to be dealt with separately from the execution of the procedure. The furthest The stated method to be carried out using a strip treatment device is currently widespread the aid of which · the reagent is applied to the audio track area in the form of a narrow edge strip. To use a

such strip treatment apparatus, the film must have the Treatment solutions are removed and dried by passing them between press rolls of the so-called Hinger type or between squeegees. Thereafter, the film is passed through the strip treatment device which, according to a known one Embodiment, having a rotating wheel that is immersed in a viscous treatment solution, which then with the help of the wheel; it is applied to the edge of the film in the form of an edge strip. The conditions under to which this strip treatment occurs are critical. So is z. B. that used to treat 16mm film Strip treatment wheel only 2.4 mm wide. If the strip treatment wheel is taking an insufficient amount of treatment mass too little of it is applied to the film, which can lead to an inferior soundtrack. On the other hand, takes If the strip treatment wheel has too much treatment solution, the edge strip applied to the film is closed wide and may cover parts of the scene building district. In this case, silver is retained and effected in the production design district a deterioration in the color image in these districts.

Another that occurs with this strip treatment technique The problem is that if the film vibrates in any way, the viscous treatment mass enters the scene area can flow, which also leads to the stated disadvantages leads. Although the strip treatment technique has been refined from year to year, the conditions are under which this procedure is carried out, is still so critical that the occurrence of some sources of error is inevitable. Sometimes these imperfections can be corrected by partially re-treating the film. In other cases it is however, the film is spoiled and must be discarded. No matter what kind of flaws in the strip treatment occur, and even if the proportion of such errors

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If the affected film is only a fraction of a percentage of the treated film, sp cause these errors but considerable costs.

The object of the invention is to find ways and means for the production of high-quality scene images and silver auxiliary images indicate the type of soundtrack, which are characterized by simplicity and economy, and a separate treatment of the silver auxiliary picture - z. B. Soundtrack district, superfluous do.

The invention is based on the surprising finding that the stated object can be achieved in a particularly advantageous manner is solvable in that photographic recording materials have a silver halide emulsion layer serving as an auxiliary layer precisely defined type with a content of weight inhibitors-releasing Compounds of precisely defined type are used and the development and work-up, in particular Bleaching and fixing of these recording materials takes place in a precisely defined manner. Recording materials with a silver halide emulsion serving as an auxiliary layer, onsschicht which contains a mercaptan-releasing compound, namely a mercaptan-releasing coupler, are already known, e.g. From U.S. Patent '3,227,554, but these have known recording materials nothing to do with films containing soundtracks and the incorporation the stated compounds only has the purpose of releasing a mercaptan which acts as a development inhibitor.

The invention relates to a photographic process for producing scene images and silver-tone track type auxiliary images in one and the same recording material, in which a photographic recording material consisting of a Layer support, at least one applied to it, for scene image recording capable, color-forming photographic

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Rope unit with at least one silver halide emulsion layer and, if necessary, intermediate and / or top layers exposed, developed into silver-containing scenes and auxiliary images and, after the silver developed in the auxiliary silver image district has been protected against fading, bleached and fixed to remove the silver halide and the remaining silver halide, which is thereby is characterized in that exposing a photographic recording material additionally comprising a group capable of HilfssilberbiMaufzeichnung Silberhaloganidemulsions ^ layer having such radiation sensitivity that no image is generated on image-wise exposure of the scene image recording unit in it, and containing a non-diffusible, Bleichinhibitor- releasing compound which, when reacted with oxidized developer compounds, forms a thiol or selenol which acts as a bleach inhibitor and carries at least one hydrophobic Eest as a ballast group, and that in de The scene recording unit of the exposed recording material creates an image consisting of dye and silver and in the auxiliary layer of the exposed recording material the silver halide is reacted with a photographic developer compound to produce a silver image and oxidized photographic developer compound before bleaching and fixing.

The invention also relates to a multilayer color photographic Recording material for carrying out the method, consisting of a layer support, three on top applied, capable of scene image recording, color-forming photographic units each having at least one silver halide emulsion layer formed in such a manner Arranged and made aware that each unit is practical sensitive to another primary color range of the visible spectrum and capable of recording practically blue, is capable of green or red light, and optionally intermediate and / or top layers, which is characterized in that the recording material in addition to the auxiliary silver image

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has recording capable silver halide emulsion layer with such radiation sensitivity that upon imagewise exposure of the scene image recording units no image is produced in it, as well as containing one non-diffusible, bleach inhibitor releasing Compound which, when reacted with oxidized developer compounds, acts as a silver bleach inhibitor, at least forms a thiol or selenol bearing a hydrophobic residue as a ballast group.

To carry out the method of the invention, a dye image and a first silver image are first recorded in the scene image recording unit then the silver halide present in the auxiliary layer to form a second silver image and oxidized photographic developing agent and finally to remove the first silver image and remaining silver halide bleached and fixed.

According to a particularly advantageous embodiment, the exposed photographic recording material with a Primary aromatic amine type color developing agent developed to form a scene record of silver and a nondiffusible dye in the The scene image recording unit or the scene image recording units, as well as an auxiliary image recording made of silver in the auxiliary layer. The formed oxidized primary aromatic amine color developing agent reacts with it the bleach inhibitor-releasing compound present in the auxiliary layer, releasing a ballast group bearing silver bleach inhibitor, which prevents the bleaching of the silver in the auxiliary image recording area. In connection At this development, the remaining silver halide and the silver that can still be bleached out are removed by bleaching and fixing, with that present in the auxiliary layer Silver is preserved and the auxiliary silver image

Q $ 8 2 Ö / 0 9 5

drawing represents.

The photographic ones which can be used in a particularly advantageous manner Recording materials according to the invention have, in addition to at least one capable of recording scenes photograph.isch.en unit with at least one, usually with one or two silver halide emulsion layers, a photographic silver halide emulsion layer capable of auxiliary image recording on, which in the scene image-wise exposure of the scene image recording units no image generated. The non-diffusible that is present in the auxiliary layer Compound generated upon reaction with oxidized primary aromatic amine type color developing agents imagewise a ballasted silver bleach inhibitor. It has proven to be particularly advantageous to use the to incorporate a non-diffusible photographic color coupler into units capable of recording scenes, that with oxidized color developing agents of the primary aromatic amine type to form a dye reacted. The color of the dye formed in this way is preferably complementary to the primary sensitization and color of light recorded by the emulsion layer in which it is incorporated. In the case of the one present in the auxiliary layer non-diffusible compound - it can be a photographic color coupler.

Very particularly advantageous photographic recording materials according to the invention are those which serve as multicolor cinema films and have a sound track. Such recording materials consist of a transparent layer support on which several, usually three, are used for the recording of scenes capable photographic units are applied, each of which has one or more, usually one or two, Has silver halide emulsion layers arranged and sensitized in such a manner that each unit

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practically compared to another primary color range of the

. Λ - ^ - L- r ,, ^ *> χ-, j ^. λ. j / ^{is sensitive at} any point in the visible spectrum, and / o is arranged a photographic silver halide emulsion layer capable of auxiliary silver image or silver tone trace recording which, due to its special radiation sensitivity, does not produce an image when the scene image recording layers are exposed. As already mentioned, the auxiliary layer contains at least one non-diffusible compound which, when reacted with oxidized color developer compounds of the primary aromatic amine type, releases a compound which acts as a silver bleach inhibitor.

According to a particularly advantageous embodiment, each scene image on the drawing layer contains a non-diffusible one photographic color coupler which reacts with oxidized color developing agents from the primary aromatic Amine type is capable of forming a dye. The dye formed in each of the layers is particularly significant advantageously a color that is complementary to the color of the wavelength range against which the the emulsion layer containing the color coupler is sensitized.

In addition to the specified scene image recording units and the The photographic recording materials can have an auxiliary layer according to the invention have a yellow filter layer. In this case, the scene image recording units and the Yellow filter layer arranged and sensitized in such a way that every scene image on the recording unit is practically opposite is sensitized to another region of the visible spectrum.

The scene image recording layers of the photographic material according to the invention are intended to be recorded from the scene images from subtractive dyes

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"Create existing images. These layers can contain dyes form whose color is complementary to that to which the layers are sensitive. So can e.g. B. the blue-sensitive layer a yellow dye image, the red-sensitive layer a blue-green dye image and the green sensitive layer is a magenta dye image form. Optionally, these layers can also be incorrectly sensitized, i. H. they can produce dyes, their Color is not complementary to the color to which the relevant layer is sensitive. Possibly these layers can serve to produce a dye or dye mixture whose density appears to be neutral.

The recording materials according to the invention are both suitable for use in the negative positive system of photography as well as for use in the inverse system of photography.

For the production of subtractive dyes, the photographic Recording materials according to the invention are developed in the presence of photographic color formers * Photographic color formers which can be used in a particularly advantageous manner are referred to as couplers. In the well-known three-color system subtractive color photography are usually used 5-pyrazolone coupler for the formation of purple dyes, phenolic couplers, including naphtholic couplers, for the formation of cyan dyes and open chain Ketomethylene coupler used to form yellow dyesa.

The photographic recording materials according to the invention may have layers to which no couplers are inherent. In this case, the recording material can be used in the presence of a KuppleB-Entwicklermaage entwiekolfc%? ®? Don _β line such Kupplor-Entvicklermano eat keeps both diffusioasfähige photograph! Sch · Sntwicklerverbindungen and the

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primary aromatic amines and diffusible photographic Color coupler. The oxidized photographic developing agent couples with the diffusible color coupler Formation of a nondiffusible dye at the sites where photographic silver halide development has taken place. Typical »in coupler developer compositions usable color couplers are z. Described in U.S. Patents 2,252,718, 2,252,243 and 2,950-970.

^% To be particularly advantageous the use of couplers has been found, which are non-diffusible, and the determined scene to the image recording silver halide layers are incorporated. The exposed photographic recording materials are then in the presence of a color developing agent of the primary aromatic amine type, e.g. B. the well-known p-phenylenediamines developed. The oxidized color developing agent produced upon reduction of the silver halide latent image couples with the couplers incorporated in these layers to form a nondiffusible dye. Typical suitable, non-diffusible photographic couplers which can be incorporated into the silver halide emulsion layers capable of scene recording of the photographic recording materials according to the invention are e.g. B. the pyrazolone couplers described in US Patents 2,343,702, 2,369,489, 2,436,130, 2,600,788 _% 3,006,759, 3,062,653, 3,311,476 and 3,419,391 and in Belgian Patent 698,354 as well as the phenolic couplers of the US Pat

2,367,531, 2,423,730, 2,474,293, 3,311,476, 3,419,390,

3,458,315 and 3,476,563, as well as the offon chain Ketomethylene coupler of the patent in the USA 2 206 142, 2 436 130, 2 728 658 and 3 4OQ 149 Type. The layers can also contain other types of couplers contain, e.g. development inhibitor-free couplers, like this z. B * in the USA patent office 3 227 554 will.

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The method and recording material according to the invention is not limited to cases where color photographic couplers are used to form color images. Rather, it is useful in any photographic system in which first and second silver images are formed and in which it is desirable to selectively remove the first silver image, e.g. B, by bleaching and fixing, under simultaneous preservation of the second silver picture.

Those in the photographic material of the invention The present auxiliary layer is only used to create the auxiliary image or record a soundtrack image. This auxiliary layer can be arranged at any point on the recording material be. So she can z. B. in the form of a light-sensitive layer, which is arranged closest to the »layer support, or it can be the furthest away from the substrate Form light-sensitive layer. Furthermore, it can be arranged between two scene image recording units, or between a scene image recording unit and a filter layer, if the recording material concerned Contains filter layers.

For reasons that are easy to understand, no latent images of the scene image recording should be formed in the auxiliary layer. Depending on the arrangement of the scene image recording units and auxiliary layers and any filter layers that may be present, various exposure methods can be used to create a scene image exposure to achieve without the auxiliary layer at the same time to expose the scenes. Provides z. B. the auxiliary layer is the light-sensitive layer closest to the support Layer and is between this auxiliary layer and the scene image Drawing units en a removable, z. B. bleachable filter layer arranged so the scene image recording layers from the emulsion side, and the auxiliary layer can be exposed through the support.

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On the other hand, the auxiliary layer represents that of the substrate is the most distant photosensitive layer and is located between the auxiliary layer and the underlying scene recording layers have a removable IT filter layer, so the scene exposure can through through the layer 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 Trap, a selective exposure of the auxiliary layer and the scene image on the drawing layers is achieved in that the auxiliary layer with regard to photographic sensitivity or spectral sensitization or with regard to both properties differ from the rest of the layers. So z. B. the auxiliary layer to be sensitized to radiation, compared to which the scene image recording layers at least are partially insensitive, e.g. B. to infrared radiation, in which case the exposure through suitable filters he follows. Optionally, the sensitization of the auxiliary layer

"to the
compared to / between two of the existing scene image recording layers is comparatively the same

be

minimal awareness /. Such areas are z. B. between the blue and green sensitive layers or the green and red sensitive layers of a color film having three color forming units of which each is primarily sensitized to a different primary region of the visible spectrum. In addition to or instead of of the spectral sensitization, the auxiliary layer can be a have different photographic sensitivity than the other layers. So z. B. the auxiliary layer is unsensitized be, d. H. it can only be achieved by the native sensitivity of the silver halide to radiation of the ultraviolet or near the blue spectral range. In this case the auxiliary layer should be less sensitive than the blue

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sensitive layer, so that they are blue-sensitive in the exposure Scene image recording layer not exposed will. Optionally, the auxiliary layer can be sensitized to one of the primary color areas of the visible spectrum be. In this case, too, the auxiliary layer should be less sensitive than the scene image on the drawing layer which has a corresponding spectral sensitivity.

According to a particularly advantageous embodiment, the multi-layer color photographic recording material has detection of the invention a scene drawing district and a Soundtrack recording area and consists of a transparent substrate on which are applied (1) three color-forming photographic images capable of recording scenes Units each having at least one silver halide emulsion layer, which are arranged and sensitized in such a way that each unit is practically opposite one other primary color range of the visible spectrum sensitive and for recording practically blue, green or » red light is capable, these color-forming units have minimal sensitization to at least a portion of the spectrum that was adjacent sensitized bridged color-forming units, and (2) one for auxiliary image or sound recording capable silver halide emulsion layer, which is sensitive to such an area of minimal sensitization, such radiation sensitivity has that, in the imagewise exposure of the scene image on drawing units, no image is produced in it, and one Has photographic sensitivity that is at least 2- in the Hegel is 2 to 15 times lower than the photographic one Sensitivity of the color-forming units of neighboring spectral Sensitization when selective exposure is carried out in the area of minimal sensitization.

These areas of minimal sensitivity between the peak sensitivities two color-forming units occur

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due to the special nature of the spectral sensitization photographic silver halide emulsions used sensitizing dyes. Such dyes lead to no sharp drop in the sensitization they impart to silver halide. So begins z. B. by a sensitization effect imparted to a certain dye more or less gradually at a certain wavelength, suffices a more or less pronounced peak value and in turn loses effectiveness more or less gradually.

In a color photographic recording material with more as a photosensitive layer, each layer is practically opposite a different primary color range of the visible Sensitized to the spectrum, d. H. compared to the blue range from about 4-00 to 500 nm, compared to the green range from about 500 to 600 nm or towards the red range from about 600 to 700 nm, whereby the sensitization of the individual Layers can overlap to some extent. So the sensitization of a first layer can be gradual decrease at a wavelength at which the sensitization a second shift begins. In some places in this area of overlapping awareness is the Sensitization effect in the two layers very close to a minimum. The specified auxiliary layer can be in the Be sensitized in a manner that is sensitive to at least such an area of minimal sensitization. If the soundtrack recording or auxiliary picture recording is copied, the exposure is carried out with light of a narrow bandwidth, the maximum intensity of which is indicated in the Area of minimal sensitization between two color-forming ones Units.

In a multilayer film with three color-forming units, each facing a different primary color range of the visible spectrum is sensitized, such a

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tiger area, minimal awareness between the "blue and green area of the visible spectrum. Depending on the type of "blue- and green-sensitive color-forming units" used sensitizing dyes, the point of minimal sensitization is usually between about 460 and 500 mn. In the specified film type, another such area occurs between the green and red areas of the visible Spectrum on. The point of minimal sensitization is again, in this one between about 550 and 590 nm depending on the type of the green and red sensitive color-forming units used sensitizing dyes.

The auxiliary layer opposite at least one such Is sensitive in the area of minimal sensitization, must also have photographic sensitivity, which is at least 2 times lower than the photographic sensitivity of the two color-forming units of adjacent ones spectral sensitization. This proves to be necessary because it is used to sensitize the auxiliary layer Sensitizing dyes used against the indicated areas of minimal sensitization likewise to none sharp drop in the sensitization they impart to the silver halide. These dyes therefore give the Auxiliary layer a sensitization, which deals with the sensitization of the color-forming units of neighboring spectral Sensitization overlaps and extends into it. To avoid the exposure of the auxiliary layer during the scene-based Exposure of those able to record scenes color-forming units, the auxiliary layer must therefore have a photographic sensitivity which is lower than that of the color-forming ones intended for scene image recording Units with adjacent spectral sensitization.

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The photographic sensitivity of a silver halide layer to a specific wavelength of light is in part dependent on the spectral sensitivity of the silver halide to this wavelength of light. If a silver halide emulsion is not sensitive to a particular wavelength of light, it is photographic Sensitivity to this wavelength of light is zero or at least much less than the photographic sensitivity of a silver halide emulsion, which is spectrally sensitized to this wavelength of light.

The auxiliary layer present in the photographic recording material according to the invention is preferably with aid of a sensitizing dye which has a peak sensitization in the range of minimum sensitivity, that between the sensitizations of two color-forming units of neighboring spectral sensitization is located, confers. Since the awareness summit in occurs in this area of minimal sensitization, the spectral sensitization and thus the photographic sensitivity falls of the auxiliary layer with respect to light of wavelengths lying on both sides of this peak gradually decreases. Conversely, the spectral sensitization and thus the photographic sensitivity of the color-forming units increases neighboring spectral sensitization to light of the same wavelengths gradually increases in the direction of their respective Awareness Summit. It thus follows that the spectral Sensitization and the photographic sensitivity of the auxiliary layer, which is almost maximal, is minimal in this area Sensitization of the color-forming units with neighboring spectral sensitization, whereas the spectral The sensitization and photographic sensitivity of these color-forming units decreases. Minimal in this area Sensitization is therefore the photographic sensitivity

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of the two color-forming units and the photographic The sensitivity of the auxiliary layer is as equal as possible.

In connection with the invention, "photographic Sensitivity "of a silver halide emulsion layer or color-forming unit means the photographic sensitivity of the same Layer or entity at the wavelength or wavelengths of the light to which they are exposed does not designate however, the maximum photographic sensitivity of the layer or unit, which may be used at other wavelengths of light can lie.

Typical suitable sensitizing dyes which can be used to sensitize the auxiliary layer to a typical region of minimal sensitization which lies between the peak sensitivities of the blue- and green-sensitive color-forming units capable of scene recording are e.g. B. 3-Ethyl-5- (i-ethyl-4 (1H) pyridylidene) rhodanine, 3-ethyl-5- (3-ethyl-2-benzothiazolinylidene) rhodanine and anhydro-3,3'-bis- (2-carboxyethyl) thiazolinocarbocyanine hydroxide. The two first-mentioned dyes are z. B. von Brooker et al in "J. Am. Chem. Soc." Volume 73, (1951), page 5326. A sensitizing dye which can be used to sensitize the auxiliary layer to a typical range of minimal sensitization which lies between the peak sensitivities of the green- and red-sensitive color-forming units capable of scene recording is e.g. B. Anhydro-3 ¹ , 9-diethyl-5-methoxy-5-phenyl-3- (3-sulfobutyl) oxaeelena carbocyanine hydroxide.

The silver halide content of the auxiliary layer can be very different, but lie in the Hegel per m ² of support surface about 0.215 bie 1.6 g (20 bie 150 mg / sq.ft.) Of silver in the form of silver halide before, even if necessary, amounts below or above de · specified range. The amount of in the auxiliary layer

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The silver halide present has an influence on the haze of the recording material and the sharpness of the observed material Image. It has therefore proven particularly advantageous to add the silver halide in the auxiliary layer in such amounts

ο use that about 0.27 to 1.1 g per m of support surface

'(25 to 100 mg / sq.ft.), Preferably about 0.32 to 0.81 g (30 to, 15 mg / sq.ft.) Silver in the form of silver halide is omitted. Contain particularly advantageous auxiliary layers

ρ
per m of support area about 0.375 to

"Silver in the form of silver halide.

per m of support area about 0.375 to 0.81 g (35 to 75 mg / sq.ft.)

The grain size of the silver halide present in the auxiliary layer can be very different. So z. B. the average grain size of the silver halide usually about 0.05 to 0.5 microns, but can also be below or above the stated range. In particular in the cases in which the auxiliary layer is only used to record the soundtrack image Used in a movie, the grain size should be as small as possible without the soundtrack area being exposed to light must be exposed to such a high intensity that the scene image on the drawing layers overexposed in the soundtrack area as this leads to a loss of resolution in the sound recording leads. The use of silver halide with a grain size of about 0.05 to 0.2 microns has been found to be particularly advantageous proven.

In the case of the silver halide emulsions used to produce the auxiliary layer can be negative developable emulsions or fogged direct positive emulsions. The emulsions can contain a wide variety of conventional silver halides, e.g. B. silver chloride, Silver bromide, silver chlorobromide, silver bromoiodide, silver chlorine obromojodi'd or mixtures thereof.

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Particularly advantageous results can be achieved when using a reversal film with an auxiliary layer that consists of a fogged, direct positive silver halide emulsion of that described in French Patent 1,520,821 Type is manufactured. Such fogged direct positive emulsions are uniformly fogged and therefore contain a latent image everywhere. This latent image is then destroyed in direct proportion to the exposure. In development in conventional known black-and-white developers a reverse image is produced, the density of which is inversely proportional the exposure encountered, d. that is, the greatest density in the unexposed areas and the lowest density in areas of strongest exposure. The use of such Direct positive emulsions are found to be very advantageous for producing a silver tone track in reversal films, since the soundtrack can be copied from a negative original instead of a positive original. The one with the production Lachmann concerned with soundtracks is well aware that soundtracks obtained from negative originals are better ones Show quality as soundtracks obtained from positive originals. The use of the specified disguised direct positive silver halide emulsions in the auxiliary layer reversal films according to the invention therefore lead to formation the higher quality negative soundtracks.

The silver opacity of the auxiliary layer of reversal cinema films formed silver image can be increased by image-wise retention of silver from an adjacent one Silver halide layer originates, the silver reduction of which is independent of the exposure. Preferably ea is in the auxiliary layer around a direct-positive emulsion layer and in the adjacent silver halide layer around a veiled or unveiled layer of a Lippmanji emulsion.

209629/0967

In the auxiliary layer there are also direct positive silver halide emulsions usable, which form the latent image predominantly in the interior of the silver halide grains, as described e.g. Am U.S. Patent 2,592,250. Such Inner grain image type emulsions are formed in the presence of a fogging developer, e.g. B. one with a Content of a hydrazine compound. 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 desired. The scene image on the drawing area of the auxiliary layer must be included Flash light treated to the development of the silver halide present in this district and the subsequent Prevent release of bleach inhibitor, resulting in preventing the bleaching of this developed silver would lead.

The photographic silver halide emulsion layer acting as an auxiliary layer of the recording material according to the invention contains, as already mentioned, at least one non-diffusible Compound which, when reacted with an oxidized developing agent, is imagewise a silver bleach inhibitor forms. This nondiffusible compound present in the auxiliary layer is preferably involved to a photographic coupler which is substituted in the coupling position with a component which is to be decoupled is capable of reacting the coupler with an oxidizing

, Color. , ". vom.primären aromatic amine type ten / developer association /. This uncoupled component is capable of then to act as or form a silver bleach inhibitor. Such bleach inhibitor releasing couplers which hereinafter referred to as "BIR" couplers, as well as other useful bleach inhibitor releasing compounds which are no couplers are described in more detail below.

209829/0987

The auxiliary layer has proven to be "particularly advantageous a scavenger for oxidized developer compounds, e.g. B. hydroquinone, for example dioctyl hydroquinone, or a photographic coupler. "Scavenger" means any compound that starts with oxidized developing agent reacts and in this way the migration of the oxidized developing agent prevented from the development site, and which further does not release a bleach inhibitor. Would the oxidized color developer connection from the point of development has taken place migrate away, it could be with a color coupler at another location, e.g. B. in one of the scene image recording units of the film, react to form a dye. The creation of such a dye at a location remote from the color development site, the developed color would be wrongly tinted Lead image. It thus follows that the auxiliary layer is the scavenger for oxidized developing agent and the BIR compound should contain at least such an amount that is sufficient to deal with the entire oxidized color developing

en
lerverbindungenj, which are formed during the development of all the silver halide present in the auxiliary layer, to react. This amount can easily be determined by the person skilled in the art.

In the Hegel iet the amount of bleach inhibitor releasing Connection (BIR connection), which is used to implement with the whole oxidized color developing agent, which is present in the auxiliary layer during the complete development Silver halide would form, greater than the amount required to release that much bleach inhibitor required iet. how to completely protect the

towards

wrapped silver «a · bleaching is needed. Bleach inhibitors of certain types can, if they are present in an amount that exceeds the amount required to completely protect the developed syllable from bleaching,

20982S / UÖ67

cause adverse effects, ζ. B. impairment of fixation, inhibition of development, unwanted reaction with oxidized color developing agent or diffusion to developed silver that is not protected by bleach inhibitor shall be. It is therefore desirable for the auxiliary layer to contain approximately that amount of BIR compound which is sufficient Bleach inhibitor component releases virtually all of the developed silver present in the sound recording to protect. This amount of BIR compound is less than that amount that is required to deal with the whole, in developing the whole in the auxiliary layer oxidized color developing agent formed from any silver halide present to react.

For these reasons, it has proven to be advantageous to add an interceptor to the auxiliary layer in addition to the BIR compound for oxidized developing agent, e.g. B. a competing, for the release of bleach inhibitor not capable couplers to incorporate. The combination of scavenger and BIR compound should be at least in such amount present, which is necessary to deal with the whole in the development of the whole present in the auxiliary layer Oxidized color developing agent formed by silver halide to react. Usually the ratio is Scavengers, e.g. B. to couplers that are not a BIR compound: BIR compound about 1: the M multiple the amount of BIR compound present. So z. B. the amount of scavenger present in the auxiliary layer often 4 to 10 times the BIR link present in this layer.

It can also serve as a guide that, as a rule, about 100 % of the developed silver can be retained if about 0.01 to 0.03 millimoles of ballasted silver bleach inhibitor are released during development.

209829/0 ** 7

2
Development of an auxiliary layer which contains about 750 mg (70 mg / sq.ft.) of silver per m of carrier surface in the form of silver halide with an average grain size of about 0.1 micron. The amount of ballasted bleach inhibitor compound that must be released to retain about 100% of the developed silver developed from different grain size silver halide can be readily determined by those skilled in the art.

If the BIR compound used is a coupler, the scavenger for oxidized developer compounds and the competing coupler may be the same type of coupler as is present in the BIR compound. Is z. B. the BIR coupler a 5-ΐνΓβζο1οη1ηιρρ1βΓ, the competing coupler can also be a 5-pyrazolone, but it can also be a different type of coupler, e.g. B. a phenolic or open-chain ketomethylene coupler act. It can thus be seen that the dyes formed in the reaction of the BIR and competing couplers are not necessarily of the same hue. Difes is due to the fact that the present in the auxiliary layer silver is not bleached and consequently absorbs all colors of light, which leads to a neutral ¹ reproduction of the auxiliary image or audio track. These dyes can be diffusible if they are to 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 should be the same as oxidized color developing agent should preferably be about the same size as that of the BIR compound. This "adaptation" reactivity with oxidized color developing agent

209829/0957

therefore follows to ensure that the appropriate amount Bleach inhibitor is released. If the scavenger is less reactive than the BIR compound, most of it reacts Part of the BIR compound with the oxidized color developing agent before the scavenger is implemented. In this case, most of the bleach inhibitor will be in one released early stage of development, in which there is still very little developed silver, to which the bleach inhibitor is released can be absorbed. On the other hand, if the scavenger is more reactive than the BIR rattle, it almost has to be entire silver halide will be developed before taking the BIR compound with oxidized color developing agent Release of a bleach inhibitor reacts. If therefore not almost complete exposure and development of the in the Auxiliary layer present silver halide is done the developed silver is not protected by bleach inhibitor and consequently during the subsequent bleaching and fixing treatments removed.

It thus follows that it is advantageous if the auxiliary layer a mixture of BIR compound and scavenger (which is, for example, a non-BIR coupler Compound can act) is incorporated and if the BIR compound and interceptor practically the same speed with the oxidized color developing agent react. Preferably the scavenger is a competing one Coupler capable of forming a nondiffusible cyan dye of at least some Part of radiation of over about 700 nm is absorbed and in this way to the infrared density caused by the auxiliary silver image contributes.

Both the BIR compound and the scavenger can be added to the auxiliary layer by a wide variety of customary known methods be incorporated. To carry out one of these

209829/0957

In known methods, an organic solvent known as a coupler solvent is used. These coupler solvents can be of the low boiling or water soluble type which are removable from the emulsion by evaporation or washing out once the coupler and solvent are dispersed in the emulsion. Optionally, the coupler solvents can also be of the high-boiling, organic, crystalloidal type which remain in the emulsion. Typical suitable low boiling point coupler solvents and methods for their use in dispersing photographic couplers are e.g. B. in US Pat. No. 2,801,170, in particular column 2, lines 3 to 32. Reference is also made to U.S. Patents 2,861,170 and 2,801,171, particularly column 10, lines 33 to 51. The high-boiling, organic, crystalloidal coupler solvents are those which are practically insoluble in water, have a low molecular weight and have a have a high boiling point (above about 175 ⁰ G at atmospheric pressure). Typical suitable solvents of this type are e.g. See U.S. Patents 2,801,171, column 10, lines 22-32, 2 94-9 360, column 2, lines 3-18, and 2,322,027, page 2, column 2, line 45 to page 3, column 2, line 6.

A person skilled in the art who wishes to tailor the emulsion which can be used to produce the auxiliary layer for specific purposes and needs can also use further suitable additives, e.g. B. sensitizing dyes and geeign | te _Q methods for their incorporation into the silver halide select /.

As a binder for the silver halide of the auxiliary layer or of the layers intended for scene recording are conventionally known photographic hydrophilic colloids, e.g. B. gelatin, usable.

200829/0957

Multilayer photographic materials are preferred with at least one photographic unit capable of recording scenes, the one or more Contains silver halide emulsion layers and a photographic silver halide emulsion layer capable of auxiliary image recording, which does not produce an image in the imagewise exposure of the scene image recording units and contains a "compound that reacts with an oxidized Color developing agent from the primary aromatic Amine type forms a silver bleach inhibitor, processed in the way that (A) the recording material with a color developing agent of the primary aromatic amine type under Forming a scene record from silver and a nondiffusible dye in the scene record layer, and a silver auxiliary image or sound recording is developed in the auxiliary layer, the oxidized Primary aromatic amine color developing agent with the bleach inhibitor precursor compound present in the auxiliary layer reacts with imagewise release of silver bleach inhibitor, and (B) the silver halide still present as well as that present after process step (A) Bleachable silver can be removed by bleaching and fixing, whereby the silver present in the auxiliary layer is retained remains and forms the silver auxiliary image or sound recording.

The processing of these recording materials can be carried out using commonly available developing devices, e.g. B. with the help of the currently commonly used, widespread, continuously operating development apparatus. The processing temperatures can be very different. Suitable treatment temperatures are e.g. B. those as they are used nowadays for processing other films of conventional known type. As a rule, these temperatures are about 20 to 60 ^° C., but can

2Q9829 / 0SS7

below »or above the specified range. Temperatures of about 25 ^° C., 40 ^° C. and 50 ^° C. have proven to be suitable for carrying out high-speed development processes.

As already mentioned, the auxiliary layer has one photographic sensitivity or spectral sensitization or both photographic sensitivity and also spectral sensitization that no image is produced in it during the imagewise exposure of the scene images on the recording units. The exposure of the auxiliary layer can be carried out before, simultaneously with or after the Scene exposure take place. The auxiliary image exposure takes place in such a way that the auxiliary or sound image is recorded at least in the auxiliary layer. Subsequent to Exposure is the recording material as indicated processed.

Although the photographic recording materials according to the invention in a particularly advantageous manner for color cinema films with a silver tone recording are they also apply to any other type of color photographic recording material containing an auxiliary silver image suitable. Since the recording material according to the invention is particularly advantageous for the production of silver-tone recordings the general processing sequence should be appropriate as well as the method by which the auxiliary silver pictures in color photographic recording materials with regard to color cinema films with silver tone recordings explained.

After exposure, the photographic recording material is processed with the aid of a photographic developing agent, preferably a color developing agent of the primary aromatic

209629 / Ü957

matic amine type. The recording material can Reverse developed by first using a black and white developer developed, and then color-developed the undeveloped, undeveloped, fogged silver halide will. The silver halide is reduced to metallic silver by the color developing agent, which oxidizes in the process will. The oxidized color developing agent formed in the auxiliary layer reacts with the photographic compounds present Couplers. If it is the photographic coupler with which the oxidized color developing agent reacts, for a competing coupler, only one dye is formed. The existing BIR connections respond In contrast, with oxidized developer compound to form a bleach inhibitor which adsorbs to the developed silver will. In the scene recording units reacts in case this phonograph! see couplers are incorporated in the Development of an oxidized color developing agent formed in these units with the latent image existing couplers to form nondiffusible dyes. Included upon completion of development the scene image recording units silver plus non-diffusible Dyes, and the auxiliary layer contains silver (as well as dye, if a non-diffusible one during development Dye was formed) to which the bleach inhibitor is adsorbed. Becomes the recording material obtained brought into contact with a bleach-fixing compound or a bleaching compound, the whole is not affected by the bleach inhibitor Protected developed silver is converted into a fixable salt and removed from the recording material. In the auxiliary layer, a bleach inhibitor is released at the points where silver was developed and to the developed silver has been adsorbed. The silver is therefore protected by the bleach inhibitor and made practically unbleachable by the course of the process, and is made from the recording material not removed. After bleaching and fixation

209829/0957

The photographic recording material contains ren or bleach-fixing non-diffusible dyes in the scene image recording units and silver (as well as Dye, if a nondiffusible dye was formed during development) in the auxiliary layer.

The amount released during development from the component released from the bleach inhibitor-releasing compound, formed bleach inhibitor can either be non-diffusible or be moderately diffusible. Is it non-diffusible, so it practically does not move away from the development point and only becomes available at the development point Adsorbs silver. In this case, only the silver developed in the auxiliary layer is blocked by the bleach inhibitor protected, and this silver is therefore the only silver that after bleaching and fixing in the recording material remains. However, if the bleach inhibitor formed is moderately diffusible, it can be released from the development site migrate away and are adsorbed on developed silver which is present elsewhere on the recording material. Since photographic silver halide layers in color films are extremely thin compared to the other dimensions of the film, the most pronounced migration is the migration from one layer to the other, but not the lateral migration within a certain layer. Therefore is the bleach inhibitor moderately diffusible, so it diffuses out of the auxiliary layer and into the above or below the Layers arranged auxiliary layer. If there is developed silver in these adjacent layers, the bleach inhibitor becomes adsorbed on this silver, which is also made unbleachable in this way.

The arrangement of an auxiliary layer on a multilayer photographic recording material increases, as already mentioned, the haze of the recording material and leads to

209828/0957

a "certain loss of sharpness of the scene image, if the exposure takes place through the auxiliary layer. This effect is due to the scattering of light caused by the silver halide grains present in the auxiliary layer is effected. The greater the silver halide content this The layer is, the greater the light scattering and, consequently, the greater the loss of sharpness. With regard to the silver halide content of the auxiliary layer should therefore be reduced for image sharpness. A decrease However, the silver halide content of the auxiliary layer lowers and reaches the silver density of the developed sound track eventually a point at which the density is no longer sufficient to produce excellent results throughout Life of the film. At this point it is still possible to make additional improvements to the sharpness of the scene to be achieved by further lowering the silver halide content of the auxiliary layer. The one required for the soundtrack Silver density in this case can be obtained if the soundtrack exposure is carried out in such a way that the scene image recording units arranged adjacent to the auxiliary layer are exposed and the bleach inhibitor formed during development is moderately diffusible, so that it wander into these adjacently arranged scene image recording units and to the silver developed in them can be adsorbed. After bleaching and fixing the recording material then contains a scene image recording of dye that is practically free of silver, as well as a sound recording of silver in both the auxiliary layer as well as in the adjacent scene image recording units.

Color photographic recording materials have in the Usually an intermediate layer between each photographic unit on. These intermediate layers often contain compounds that react with oxidized color developer compounds.

209829/0957

yaw. Such compounds are usually used as scavengers for oxidized color developing agents and are incorporated into these intermediate layers in order to Migration of the oxidized color developing agent from the development site in one layer to an adjacent one Layer where the developer compound with a coupler present there producing a false color shade can react to avoid. Typical suitable such scavengers are e.g. B. Octy! Hydroquinone, dioctyl hydroquinone, p-aminophenols, hydrazines, ascorbic acid derivatives and compounds other type, such as this z. B. in U.S. Patents 2,403,721, 2,675,314, 2,356,486, 2,360,290, 2,701,197, 2 704 713, 2 728 659, 2 732 300 and 2 735 765. It was found that moderately diffusible bleach inhibitors through interlayers containing such scavengers into adjacent silver halide emulsion layers migrate and can be adsorbed on the silver developed there in the specified manner.

Typical suitable procedures for processing exposed photographic recording materials with scene image recording and auxiliary silver image or sound recording layers of the specified type are given below.

The processing of an exposed photographic negative-positive recording material, the scene recording layers of which couplers are incorporated is carried out as follows :

1. Color development

2. (A) bleach-fix or (B) bleach and fix.

An exposed photographic material incorporating couplers can be reverse processed as follows:

209829/0957

-e- 2153576

1. Black and white development

2. Stop bath

3 Color development of the remaining, undeveloped, veiled silver halide

4-, stop bath

5. (A) bleach-fix or (B) bleach and fix

Should the reversal film for the production of a cinema film with a silver tone track are used, the auxiliary layer must be in the scene design district may be obscured so that it will be fully developed during black and white development. These Measure is taken to avoid any development and the resulting bleach inhibitor formation in the scene area of the auxiliary layer should be avoided during color development as it is undesirable to retain silver in the setting area of the film.

In the case of the BIR compounds which can be used in a particularly advantageous manner are couplers which, apart from the bleach inhibitor component, are made up of any Remainder may exist, which has an active site which reacts with an oxidized color developing agent of the primary aromatic amine type and at this active site with a bleach inhibitor formation capable component can be substituted, and its reactivity towards the oxidized color developing agent retains when it is substituted in the manner indicated. Remnants of the most varied types are for this Purpose usable. Residues of photographic couplers have proven to be particularly advantageous, e.g. B. Remnants of 5-pyrazolone couplers, phenolic couplers including Gt-naphthol couplers and of open-chain ketomethylene couplers, these coupler residues react with color developing agents of the primary aromatic amine type, usually below Formation of purple, blue-green or yellow dyes. These

209829/0957

Couplers are substituted in the coupling position with a component which forms a bleach inhibitor and represent in in this case a BIR coupler, or if this remainder none Coupler is a BIR compound. The coupling position of photographic couplers is known to those skilled in the art. The 5-pyrazolone coupler residues couple on the carbon atom in ^ - position, the phenolic coupler radicals couple on the carbon atom in

coupler

4-position and the open-chain ketomethylene residues couple on the carbon atom forming the methylene component, which z. B. can be represented by the following formula

Il

-C-CH ₂ -

where * denotes the clutch position.

In connection with the invention, "non-diffusible Bleach inhibitor-releasing or BIR compound "means a compound which meets the following requirements: If such a combination of a veiled gelatin-silver chlorobromide muleion, which is about 80 molar in terms of chloride and 20 molar in terms of bromide, and the emulsion obtained is applied to a layer support consisting of a cellulose triacetate film in the manner that per m of support surface 1.5 g of gelatin (140 mg / sq.ft.) and 0.75 S silver (70 mg / sq.ft.) are omitted, and the resulting emulsion layer also contains an oxidized scavenger Developer compounds that have practically the same reactivity with oxidized developer compound as the BIR compound with all of the BIR compound and scavenger present being sufficient to with virtually all of the Development of practically all of the silver halides present to react formed oxidized developer compound,

209I29 / 09S7

and this film sample is treated with a color developer from im Example 1 given below developed to form a silver image and oxidized Developer compound so will when the BIR compound is present in an amount sufficient to cause the reaction

2 with oxidized developer compound per m of support area approximately 0.05 ^ to 1.1 (0.005 to 0.1 / sq.ft.) Millimoles with ballast group to form a bleach inhibitor that inhibits the bleaching of a sufficient amount of developed silver, «A an infrared density measured at 900 mn of at least

obtain
0.80 if the developed silver is treated with a bleach-fix solution of the following composition for 90 seconds at a temperature of 25 ^{0 C:}

NaFeEDTA * (I3% Fe) Na ₂ SO ₅

NH ₄ SCN Na ₄ EDTA *

60 G 12th e 12th S. 7th S. 200 ml 1 liter 6, 68

Ammonium thiosulfate (60% solution)

made up to pH value with water

* EDTA · Ethylenediaminetetraacetic acid

The weight ratio is used to perform the specified test chosen from competing coupler to BIR compound so that that the optimal amount of bleach inhibitor is released under the specified conditions.

It was found that organic compounds that are in particular advantageously as ballast group-containing bleach inhibitors of the specified type are ^ thiol- and selenol-containing Are compounds that are associated with a hydrophobic component, e.g. B. a medium to long chain alkyl chain substituted

209829/0957

are or contain one. One of the tasks of this Components is to act as a ballast group, with the help of which the diffusion ratei of the ballast group Silver bleach inhibitor in the hydrophilic colloid of the silver halide emulsion layers of the recording material are controllable.

Typical suitable compounds of this type are e.g. B. mercapto- and selenol-substituted alkanoic acids, especially 2-mercaptoalkanoic acids, thiol- and selenol-substituted, ballasted aryls, e.g. B. alkyl and alkylamidothiophenols and thionaphthols, ballasted thiol and selenol substituted heterocyclic compounds with at least one nitrogen atom, e.g. B. Alkylamidomercaptobenzoxazole, Alkyl amidobenzothiazole-, Alkylamidomercaptobenzimidazole, Alkylamidomercaptothiadiazoles, alkylthiomercaptothiadiazoles, Alkylamidomercaptotriazoles, 1-alkylamidophenyl-5-mercaptotetrazoles and ballasted mercaptoquinolines, e.g. B. alkylamido and alkyl mercaptoquinolines, as well as ballasted thiocarboxylic acids, z. B. alkyl and alkylamidothiobenzoic acid.

The use of bleach inhibitor-releasing agents has proven to be particularly advantageous Couplers, d. H. BIR couplers that the following general formula has been proven:

SRC

where mean:

KUP a photograph! See coupler component necessary for implementation with an oxidized aromatic primary amine type color developing agent to form a dye is,

209629/0967

a »0, 1, 2, 3, 4, 5 or 6, X is a sulfur or selenium atom,

R is a nitro radical; a halogen atom, ζ. Β. Chlorine, bromine, fluorine or iodine atom; an optionally substituted alkyl radical having 1 to 22 carbon atoms, preferably 8 to 18 carbon atoms, e.g. B. a methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, isoamyl, tert-amyl, cyclopentyl , Hexyl, cyclohexyl, cyclohexadienyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl or octadecyl radical; Haloalkyl radical, e.g. B. fluoroalkyl, chloroalkyl or bromoalkyl radical, for example chlorooctyl, bromododecyl or fluorotetradecyl radical; Sulfoalkyl radical, e.g. B. SuIfohexyl, sulfooctyl or sulfododecyl radical; Sulfatoalkyl radical, e.g. B. sulfatodecyl or sulfatotetradecyl radical; Alkylsulfonylalkyl radical, e.g. B. Äthylsulfonylbutylrest; Cyanoalkyl radical, e.g. B. cyanohexyl, cyanooctyl or cyano decyl radical; Carboxyalkyl radical, e.g. B. Oarboxyhexyl, carboxydecyl or carboxyhexadecyl radical; Aralkyl radical, e.g. B. benzyl, phendodecyl or tolyldodecyl radical; Alkoxyalkyl radical, e.g. B. Octoxyhexyl, butoxyhexyl or Äthoxydecylrest; Aryloxyalkyl radical, e.g. B. phenoxymethyl or phenoxyethyl radical; Alkoxyaralkyl, e.g. B. methoxyphenylmethyl or .Butoxyphenylhexylrest; Acyloxyalkyl radical, e.g. B, benzoyloxyhexyl or acetoxybutyl radical; Alkoxycarbonylalkyl radical, e.g. B. butoxycarbonylhexyl radical; Ary1oxycarbonylalkyl radical, ζ. B. Phenoxycarbonyläthyl- or Ohlorophenoxycarbonylbutylrest; Alkylamidoalkyl radical, e.g. B. hexanamidobutyl or octanamidopropyl radical; Arylamidoalkyl radical, e.g. B. Phenylamidoäthyl- or Methylphenylamidobutylrest; furthermore an optionally substituted aryl radical with optionally fused-on aromatic rings, e.g. B, phenyl, naphthyl, anthracenyl,

209829/0957

or phenanthrenyl radical; Haloaryl radical, e.g. B. chlorophenyl, Trichlorophenyl, dibromophenyl, fluorophenyl, "or chlorotolyl radical; sulfoaryl radical, for example sulfophenyl radical; SuIfatoaryl radical, e.g. B. sulfatophenyl radical; Nitroaryl radical, z. B. nitrophenyl or dinitrophenyl radical; Cyanoaryl residues, e.g. B. cyanophenyl or cyanonaphthyl radical; Carboxyaryl radical, e.g. B. carboxyphenyl or dicarboxypiienyl radical; Alkaryl radical, e.g. B. tolyl, butylphenyl, Decylphenyl, diethylphenyl or trifluoromethylphenyl radical; Aralkaryl radical, e.g. B. Benzylpiienyl- or Naphthylmethylphenylrest; Alkoxyaryl, e.g. B. Octoxyphenyl or methoxyphenyl radical; Aryloxyaryl radical, e.g. B. phenoxyphenyl or phenoxynaphthyl radical; Acyloxyaryl radical, e.g. B. Benzoyloxyphenyl or acetyloxyphenyl radical; Alkoxycarbonylaryl radical, z. B. Ithoxycarbonylphenylrest; Aryloxycarbonylaryl radical, z. B. phenoxycarbonylphenyl or methylphenoxycarbonylnaphthyl radical; Alkylamidoaryl radicals, e.g. B. Acetamidoph.enyl-, Amylamidophenyl, di-t-amylamidoplienyl, hexanamidophenyl, Heptanamidoplienyl, octanamidophenyl, nonanamidophenyl, Decanamidophenyl, undecanamidoplienyl, Dodecanamidophenyl, tridecanamidophenyl, tetradecanamidoaryl, Pentadecanamidoplienyl, heptafluorobutanamidoplienyl, or Oarboxycyclopentanacetamidophenylrest; Cycloalkyliminosulfonylaryl radical, z. B. piperidinylsulfonylphenyl-, azetidinylsulfonylphenyl-, Pyrrolidinylsulfonylphenyl or indolinylsulfonylphenyl radical; also a thio residue with 3 up to 22 carbon atoms, ζ. B. alkylthio radical, ζ. Β « Propylthio, hexylthio, octylthio or dodecylthio; Carboxyalkylthio, e.g. B. Carboxybutylthio or Garboxyhexylthioest; Arylthio radical, e.g. B. phenylthio, naphthylthio or methylphenylthio; Alkylcarbonylalkylthio radical, z. B. Methylcarbonyläthylthio- or Butylcarbonylpropylthioest; Alkylcarbonylarylthio, e.g. B. Methylcarbonylphenylthio-, Hexylcarbonyltolylthio or benzylcarbonylphenylthio; Arylcarbonylarylthio radical, e.g. B.

200120/0857

Phenyicarb0n7lph.enylth.i0rest; Arylcarbonylalkylthio radical, ζ. B. phenylcarbonylmethylthio radical; also an amido radical with 4 to 22 carbon atoms, ζ. B. alkylamido radical, ζ. B. hexanamido, heptanamido, octanamido, decanamido or heptafluorobutanamido radical; Arylamido radical, z. B. benzylamido radical; Alkarylamido radical, e.g. B. Methylbenzylamido, butylbenzylamido, hexylbenzylamido or decylbenzylamido radical; Aralkylamido, e.g. B. Phenacetamido, Phenbutanamido or tolylhexanamido; Aryloxyalkylamido radical, e.g. phenoxyacetamide, naphthoxyacetamido or di-t-amylphenoxyacetamido; also a carbonyl radical, ζ. B. alkylcarbonyl radical, ζ. B. butylcarbonyl or heptylcarbonyl radical; Aryloarbonyl radical, e.g. B. phenyl carbonyl or naphthyl carbonyl radical; Alkoxycarbonyl radical, z. B. ithoxycarbonyl or butoxycarbonyl radical; Aryloxycarbonyl radical, e.g. B. phenoxycarbonyl or Naphthoxycarbonyl radical; also a carbamoyl radical, ζ. Β. Alkylcarbamoyl radical, ζ. B. butylcarbamoyl or hexylcarbamoyl radical; Arylcarbamoyl radical, e.g. B. Phenylcarbamoyl or naphthylcarbamoyl radical; also an alkoxy radical, ζ. Β. Ethoxy, butoxy, octoxy or benzoxy radical; as well as one Aryloxyreat, ζ. B. phenoxy or toluoxy, and

A is a carbonyl radical of the formula J> C «O; Thiocarbonyl residue of Formula ^ .C-S; Oarboxymethylene radical of the formula ^ CH-GOOH; carbocyclic ring with 5 to 6 carbon atoms, which can be part of a fused ring structure, e.g. B. Cycloalkylene radicals, e.g. B. Cyclopropylene, cyclobutylene, Cyclopentylene or cyclohexylene radicals; Cycloalkenylene residues, z. B. Cyclopropenylen-, Gyclobutenylen-, Gyclopentenylen-, Cyclopentadienylene, cyclohexenylene or cyclohexadienylene radicals, or arylene radicals, e.g. B. ^ phenylene, naphthylene or

' * ' ίΟ- _% vorzugaweiie 5- or oaer o-anthrylene radicalsj a 3- to / membered heterocyclic ring with at least one carbon atom and 1 to 5 atoms, which are composed of nitrogen, oxygen, sulfur or

209829/0967

- * j- 216357?

Selenium atoms exist, further carbocyclic or heterocyclic rings condensing onto this ring can be, e.g. B. an oxirenyl, furanyl, benzofuranyl, Isobenzofuranyl, dibenzofuranyl, oxazolyl, benzoxazolyl, Isoxazolyl, benzisoxazolyl, oxadiazolyl, benzoxadiazolyl, 1,2-pyranyl, 1,4-pyranyl, 2 (H) benzopyranyl, 4- (H) -Benzopyranyl-, dioxolyl-, methylenedioxybenzenes-, 1,2-oxazinyl-, 1,3-oxazinyl, 1,4-oxazinyl, morpholinyl, 1,3-dioxolanyl-, 1,3-oxathianyl-, 1,4-oxathianyl-, 1,2-dioxa-

-, 1,4-Dioxanyl-, Dioxanenyl-, Dioxadi- "
-, indolyl, isoindolyl, garbazolyl,

Pyrrocolinyl, acridinyl, phenanthridinyl, 2-imidazolinyl, 3-imdiazolinyl, 4-imidazolinyl, pyridyl, pyridazinyl, Cinnolinyl, phthalazinyl, quinoxalinyl, pyrimidinyl, pyrazolo ^ "" 3,4-d_7pyrimidinyl, hypoxanthinyl, benzopyrimidinyl, Pyrazinyl, ohinoxalinyl, phthalazinyl, quinolinyl, Isoquinolinyl, phenazinyl, phenoxazinyl, phenothiazinyl, Purinyl, pteridinyl, 1,3,5-3lriazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, triazolyl, benzotriazolyl, Tetrazolyl, triainthionyl, 1 (H) azepinyl, piperidinyl, Imidazolidinyl, quinolizidinyl, thionyl, benzothienyl, Isobenzothienyl, dibenzothienyl, thiazolyl, benzothiazolyl, Isothiazolyl, benzisothiazolyl, thiadiazolyl, benzothiadiazolyl, 1,2-dithiolyl, 1,3-dithiolyl, 1,3-oxathiolyl, Thianthrinyl, thiamorpholinyl, 1,4-thianinyl, 1,4-dithianyl-, 1,4-dithiadienyl-, selenazolyl-, Benzoselenazolyl, isoselenazolyl, benzisoselenazolyl, Selenadiazolyl or benzoselenadiazolyl ring,

where R is not a carbonyl, carbamoyl or amido radical, when A represents a carbonyl or thiocarbonyl radical, and

Ί Ί

where the grouping R- (-A-) a component with a

Molecular weight from 125 to 1000, preferably from 175 to represents and preferably no more than a solubilizing agent

208829/0357

Group, ζ. Β. Has carboxy group, unless the specified grouping a hydrophobic component, e.g. B. contains a long-chain alkyl radical or an aryl radical, and

furthermore, when A is a carbocyclic or a heterocyclic Ring represents, a hydrophobic component is bound to this ring, e.g. B. the one to complete a 5- or 6-membered carbocyclic or heterocyclic ring fused to the specified ring Atoms, or an alkyl radical with 8 to 18 carbon atoms, an alkylamido radical with 8 to 18 carbon atoms, or an aryl radical, z. B. phenyl naphthyl or alkylamidoaryl with 8 up to 18 carbon atoms in the alkyl component, or more these hydrophobic residues, the overall effect of which in terms of imparting a hydrophobic character is the same as him two alkylamido radicals with 3 to 12 carbon atoms and two alkylamidoaryl radicals with 3 to 12 carbon atoms in the Cause alkyl component.

It has been found to be particularly beneficial when the

1 1
Grouping R-AX with oxidized aromatic

et

Color developing agent is unable to react.

Numerous molecular weight heterocyclic compounds less than 100 (excluding the mercapto or selenol group), e.g. B. those from the British patent 1,138,842 known compounds were not found to be bleach inhibitors, but rather as bleach accelerators. Compounds of this type do not fall under the definition given for bleach inhibitors.

According to a particularly advantageous embodiment of the invention, BIR couplers are used which are used to release Bleach inhibitor-forming components which are

1 1 as can be seen from the given formula KUP-X-A -R, is an organic compound or its salt, enables

209829/0957

and which have an acidic TMoI or selenol. the Acidity of the thiol or selenium oil groups can be determined by the remainder to which these groups are attached, e.g. B. by a heterocyclic or carbocyclic ring. Optionally, others to which the thiol and A residue bearing selenol groups is given by bonded groups which impart acidity. So gives z. B. a carboxyl group attached to a Carbon sits which is adjacent to the carbon atom bearing the specified groups, e.g. B. 2-mercaptolauric acid, the desired acidity. Other type of electron withdrawing groups, e.g. B. ÜTitroreste and halogen atoms, can the thiol and selenol groups also have an acidity to lend.

To carry out the process of the invention, the use of bleach inhibitor-releasing couplers has proven itself the following formulas have proven to be particularly advantageous:

A. 2-mercaptobenzoxazoles of the formula

O _(H ™ _ 2 -N) -1 || y> S-Kup

B. 2-mercaptobenzothiazoles of the formula

S-KUP

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C. 2-mercaptobenzimidazoles of the formula

S-KUP

D. 2-mercaptothiadiazoles of the formula

N N

KUP-S-C G-Z-R '?

E. 2-mercaptotriazoles of the formula

N - N _n

Ii Il °

kup-s-c c-n-c-e

n / h

F. i-Ph.enyl-5-mercaptotetrazole of the formula

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where mean:

ΛΓ) ΛΑ AO AC.

E, R, R and R ^lp alkyl radicals with 1 to 17, preferably up to 12 carbon atoms,

14th
R ^ and R are alkyl radicals with 5 "to 17, preferably 8 to 12

Carbon atoms,

Z is a sulfur atom or the grouping -NHCO-, η β 1, 2, 3, 4 or 5 *, preferably 1, and

KUP a photographic coupler which is substituted in its coupling position with the indicated thio radical.

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

I. i-Hydroxy-4- / ~ 1- (3-decanamidophenyl) -tetΓazol-5-ylthio_7-N- (2-n-tetradecyloxyphenyl) -2-naphthamide

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

III. i-Hydroxy-4- (5-decanamido-1,3-benzimidazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide

IV. 1-Hydroxy-4- (5-nonanamido-1,3-benzoxazol-2-ylthio) -2 - / ^ - (2,4-di-tert-amylphenoxy) -n-butyl_7-naphthamide

V. 1-Hydroxy-4- (5-nonanamido-1,3-t> enzothiazol-2-ylthio) -2- / Ä - (2,4-di-tert-amylphenoxy) -n-butyl_7-naphthamide

VI. <= r- (pivalyl) -CT - (5-nonanamido-1,3,4-triazol-2-ylthio) -2-chloro-5 - / "Y - (2,4-di-tert-amylphenoxy) butyramido 7-ecetanilide

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VII. 1-Hydroxy-4- (4-nonanamidodiazet-3-ylthio) -Ii- (2-n-tetradecyloxyphenyl) -2-naphthamide

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- / 5 - (2,4-di-tert-amylphenoxy) -n-butyl_7-naphthamide

X. 1-Hydroxy-4- (4-dodecanamidocyclohexen-1-ylthio) -2- / δ - (2,4-di-tert-amylphenoxy) -n-butyl_7-naphthamide

XI. cc- (pivalyl) -cc- (4-nonanamidophenylthio) -2-chloro-5 - / "V * "(2,4-di-tert-amylphenoxy) -butyramido ^ / - acetanilide

XII. OC- (PiVaIyI) -GC- (dodecanoic acid-2-ylthio) -2-chloro-5- / ~ y - (2,4-di-tert-amylphenoxy) -butyramido_7-acetanilide

XIII. 1-Hydroxy-4- (4-octylbenzoylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide

XIV. 1-Hydroxy-4- (5-decylthio-1,3,4-thiadiazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide

XV. cc - (pivalyl) -cr- (benzophenonthio) -2-chloro-5 - / "y - (2,4-di-tert-amylphenoxy) -butyramido_7-acetanilide

XVI. ■ i-Hydroxy ^ -C ^ -decylcarbamoyl-1,3-benzimidazol-2-ylthio) -2- ^ Ä - (2,4-di-tert-amylphenoxy) -n-butyl_7-naphthamide

XVII. 1-Hydroxy-4- (6-decyloxy-1,3-benzoxazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide

XVIII. er (pivalyl) -cr- (5-phenoxy-1,3-benzothiazol-2-ylthio) -2-chloro-5 - ^ "y - (2,4-di-tert-amylphenoxy) -butyramido_7-acetanilide

209629/0957

XIX. 1- {4- / α - (3-Pentyldecylphenoxy) -butyramido 7-phenyl} -3-ätIioxy-4- (5-nonanamido-1,3 _t 4-thia- & iazol-2-ylthio} -5-pyrazolone

XX. 1-Hydroxy-4- / ~ 1- (3-decanamidophenyl) -tetrazol-5-ylseleno_7-N- (2-n-tetradecyloxypienyl) -2-naphthamide

XXI. 1-Hydroxy-4- (5-octanamido-1,3-benzimidazol-2-yl thi ο) -IT- (2-n-t e t r ade cyl oxyplieny 1) -2-naph.thamid

XXII. 1-Hydroxy-4- (5-nonanamido-1,3- "benzimidazol-2-yl thio) -E- (2-n-tetradecyloxyph. Enyl) -2-naphth.amide

XXIII. 1-hydroxy-4- (5-undecanamido-1,3-benzimidazol-2-ylthio) -W- (2-n-tetradecyloxyph.enyl) -2-naphthamide

XXIV. 1-Hydroxy-4- (5-dodecanamido-1,3- "benzimidazol-2-ylthio) -N- (2-n-tetradecyloxypiienyl) -2-naphthamide

XXV. 1- (2,4,6-a? Richlorophenyl) -3- {3 - / "ct - (2,4-di-tertamylphenoxy) acetamido_7benzamido} -4- / ~ 1- (3-decanamidophenyl) tetrazol-5-ylthio_7-5-pyrazolone

XXVI. α - {3- / ~ cc - (2,4-Di-tert-amylphenoxy) butyramido_7-benzoylj - a- / ~ 1- (3-nonanamidoplienyl) -tetrazol-5-ylthio_7-2-methoxyacetanilide

XXVII. 1- (2,4,6-Trichlorophenyl) -3-pentadecyl-4- / ~ 1- (3-undecanamidophenyl) -tetrazol-5-ylthio_7-5-pyrazolone

XXVIII. 4- ^ "i- (3-Decanamidophenyl) tetrazol-5-ylthio_7-phenol

XXIX. 5-methoxy-2- ^ cc- (3-n-pentadecylphenoxy) butyramido_7-4 - ^ "1- (3-octanamidophenyl) tetrazol-5-ylthio_7-phtnol

XXX. 1-L 4 ~ / "cc- (2,4-Di-tert-amylphtnoxy) butyramido_7-phenyl} -3- (1-pyrrolidine) -4 - ^ "" 1- (3-decanamidophenyl) tetrazol-5-yltiiio_7-5-pyrazolone

200829/0957

XXXI. α-Benzoyl-er / ~ 1- (3-decanamidophenyl) -tetrazol-5-ylthio_7acetophenone

XXXII. 1-phenyl-3-octadecylamino-4 - / ~ 1 - (3-decanamidophenyl) tetrazol-5-ylthio J7-5-pyrazolone

XXXIII. 1-Hydroxy-4-- / "~ 3-nonanainidophenyl) -tetrazol-5-ylthio__7-3 ', 5' -di-carbomethoxy-2-naph.th.anilide and

XXXIV. GC- (2-Furoyl) -cc- / ~ 1- (3-dodecanamidophenyl) -tetrazol-5-ylthio_7-3 y 5-disulfoacetanilide, dipotassium salt

The bleach inhibitor-releasing agents which can be used according to the invention Compounds and couplers are known compounds or similar to them and are customarily known to those skilled in the art Process producible. So are z. B. those described in US Pat. No. 3,227,554 for the preparation of thioether couplers Synthetic methods applicable.

To carry out the process of the invention, non-diffusible bleach inhibitor-releasing hydroquinones, ie so-called BIR hydroquinones, can also be used. "Hydroquinone" also refers to naphthoquinones and substituted hydroquinones. The use of BIR hydroquinones which have a hydrophobic group which is bonded to the aromatic nucleus via a sulfur (- S -) or seleno (- Se -) bridge on the hydroquinone has proven to be particularly advantageous. These compounds liberate an acidic thiol or selenol on reaction with oxidized developer compounds (black and white or, preferably, color developer compounds of the primary aromatic amine type, as described, for example, in Mees and James "The Theory of the Photographic Process" MacMillan Co., 1966 , Pages 278 to 311).

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

209829/0957

Ί Ί
wherein X, A and H have the meaning given and wherein

also mean:

and R _x “hydrogen atoms or in an alkaline medium abs | foldable masking groups, e.g. B. Aeylreste, for example acetyl, mono-, di- or trichloroacetyl, mono-, di- or trifluoroacetyl or perfluoroacyl (z. B. -butyryl-) - radicals or pyruvyl, alkoxalyl, nitrobenzoyl or gyanobenzoylreete , and

% 1 and ^R 42 ^f ^ ^r ^ ^B - ^cil alone Wasserst off atoms or optionally substituted alkyl groups of the meanings indicated for R ^, or

RjiQ and R ^ together are the atoms required to complete a fused-on benzene ring.

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

• 2,3-Dimethyl-5- / ~ 1- (3-nonanamidophenyl) -tetrazol-5-ylthio_ / hydroquinone,

2,3-Dimethyl-5- (5-decanamido - 1,3, ^ -thiadiazol-2-ylthio) -hydroquinone

209629/0957

3-butyl-5- (5-decanamido-1,3-benzimidazolyl-2-ylthio) hydroquinone,

3-octyl-5- (5-nonanamido-1,3-benzothiazol-2-ylthio) -hydroehinσn,

2,3-dimethyl-5- (1-carboxy-4-decanamidocyclohexylthio) hydroquinone,

2,3-Diethyl-5- (4-dodecanamidocyclohexen-1-ylthio) hydroquinone and

2,3-Diethyl-5- / ~ 1- (3-decanamidophenyl) tetrazol-5-ylseleno_7-hydroquinone.

The BIR hydroquinones are chemically related to the thio-substituted ones Development inhibitors of the type described in U.S. Patent 3,364,022 and they are similar to Process as described in the specified patent can be produced.

Further bleach inhibitor-releasing compounds which can be used according to the invention are, for. B. in British patent specification Λ 224 555 and the corresponding Belgian patent specification 713 448, these are compounds in which the -SY group of the structural formula listed on page 2 of the specified British patent is replaced by the specified grouping - X- (A) -R.

With the aid of the method of the invention, both the bleaching caused by bleaching compositions and by the bleach-fixing compositions are removed which prevents sound recordings. Bleaching compounds contain z. B. potassium dichromate or potassium ferricyanide as an oxidizing agent. Bleach-fix compositions contain both an oxidizing agent, e.g. B. an iron salt of EDTA, as well as a SiI overhalide solvent. In bleach-fixing, the silver is oxidized into one with the aid of a single treatment solution Silver salt, which then from the recording material

209629/0957

Will get removed. In contrast, lead acid compounds are only able to oxidize silver to a silver salt. The formed silver salt and any silver halide still present are then removed by treatment with a separate fixing bath.

As a rule, bleaching compounds are stronger oxidizing compounds than Bleach-fixing compositions. It has therefore proven to be particularly advantageous if the material formed during color development The bleach inhibitor component is comparatively less hydrophilic if the scene image is on drawing silver with a bleaching compound is to be oxidized. In this case, for. B. compounds can be used with a comparatively hydrophobic Component, e.g. B. a long chain fatty acid are substituted.

Silver tone recordings are also made using the method of the invention and films whose color images are of neutral density can be produced. Neutral density images are off a coupler or a mixture of couplers which can be prepared with the formation of dyes or dye combinations react that appear to be of neutral density. As with color images, Neutral density images remove the silver of the scene recording by bleaching and fixing. The silver tone record can be retained in films of the specified type by using an auxiliary layer that releases a bleach inhibitor Compound or a bleach inhibitor-free releasing agent Contains couplers which result in a neutral density film whose scene is recorded from a dye or a dye mixture and its sound recording consists of silver.

Be "non-diffusible", or "non-diffusible" with the coupler and the derivatives derived therefrom Auedruck, has the usual meaning in the color photograph

201829/0967

and is applied to materials which practically do not migrate through photographic hydrophilic colloid layers, e.g. B. Ge-latin layers, especially during treatment in aqueous alkaline solutions. That has the same meaning Term "immobile" or "motionless". The expressions "Diffusible" and "mobile" have the opposite meaning. With "moderately diffusible" and "moderately mobile" refers to compounds that migrate through photographic hydrophilic colloid layers, but their diffusion rate is noticeably slower than that of compounds to be designated as diffusible or mobile, their Diffusion rate, on the other hand, is significantly greater than that of non-diffusible or immobile compounds.

The invention is illustrated in more detail by the accompanying drawing, in the represent

1 shows the exposure and processing of a photographic recording material according to the invention in a scheme, and

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

In Fig. 2, a typical movie with soundtrack is shown schematically. The soundtrack shown in the soundtrack area 11 is one of the type of different districts. The image fields shown in the scene design district 12 contain the individual Production photography recordings. The gear perforations 13 are used for transporting the film through the equipment used in connection with motion picture production and viewing will.

In Fig. 1, the photographic material according to of the invention during individual stages of the invention

209829/0957

Process for the production of color scene image recordings and silver tone recordings shown schematically in cross section. The recording material consists of the transparent Layer support 22, on which are arranged one above the other a blue-sensitive, for the formation of yellow dyes Gelatin-silver halide capable layer 23, a red-sensitive gelatin-silver halide layer capable of forming cyan dyes 24, a green-sensitive gelatin-silver halide layer capable of forming purple dyes 25 and a cyan-sensitive gelatin-silver halide layer capable of forming cyan dyes in the form of the auxiliary layer 26 with a content of bleach inhibitor-free establishing connections. The auxiliary layer 26 is sensitized in such a way that its sensitivity peak is around 480 nm. The photographic sensitivity of layer 26 is about 0.4 log E less than that of the less sensitive layer of the two layers 23 (blue sensitive) and 25 (green sensitive) when exposed at 480 nm. To simplify the presentation, the usual known adhesive, Intermediate and top layers have been omitted from the drawing.

In stage 1, the exposure of the recording material takes place represented by the negative original, with the original only in the form of a single pictorial layer for the sake of simplicity 21, which is applied to the transparent layer carrier 20, is shown. The exposure for the scene image recording will be with white light, and exposure for sound recording is with blue-green light, the intensity of which is at its maximum about 480 μm and the bandwidth of which is about 20 nm at half height. In practice, this can be the case Original used for exposure to a multilayer, multicolored recording material or by a Acting scene seen by camera lens. In addition, the scene image recording and the soundtrack recording are located in the practice.

209929/096?

-% - 216357S

tion in the Hegel on separate originals, with each of these originals separate exposures are made shortly one after the other.

In step 2, the state of the exposed recording material becomes after the development of the latent image with the aid of a color developer. The layers 23a, 24a and 25a contain silver and dye images in the scene area 210. No exposure has taken place in the scene area 29 of these layers, so that no latent image is formed either became. Silver halide is therefore present in region 29 of these layers. The auxiliary layer 26a is due to its special photographic sensitivity and spectral sensitization is not exposed and therefore contains both im District 29 and 210 of the silver halide production design district. The layers 25a, 25a and 26a get due to them special photographic sensitivity and spectral sensitization a soundtrack exposure and contain silver and Dye images in the soundtrack districts 27 »as well as silver halide in the soundtrack district 28.

Layer 26a contains a bleach inhibitor releasing agent Coupler which interacts with the oxidized color developing agent formed in this layer during development of the latent soundtrack image reacts to release a component which forms a bleach inhibitor. According to the in Fig. 1 In the embodiment shown, the bleach inhibitor that forms is a moderately diffusible compound, which not only to the one in district 27 of layer 26a developed silver is adsorbed, but also diffused a piece into the layer 25a of the region 27 and attached to the developed silver present there is adsorbed. The layer 24a has received no soundtracking and therefore has both in the soundtrack districts 27 as well as 28 silver halide.

20S829 / 09S7

Level 3 represents the state of the recording material after the developed recording material is brought into contact with a bleach-fixer and then washed became. Layers 23b, 24b and 25b in the scene area are now clear because of the silver halide present there was fixed out. The scene area 210 of these layers contains dyes, since the developed silver present there was removed by bleaching and fixing. The auxiliary layer 26b is now clear in the scene areas 29 and 210, since the silver halide present there has been fixed. All four layers in audio track area 28 and layer 24-b in District 27 is now clear because the remaining silver halide has been fixed out. The layer 23b and the lower part of the Layer 25b in the soundtrack area 27 contain dye because the developed silver present in these layers is caused by bleaching and fusing was removed as it was not protected by the bleach inhibitor formed during color development became. The layer 26b and the upper part of the layer 25b contain silver and dye in the soundtrack area 27, da the silver present there had been protected by the bleach inhibitor formed during color development.

The developed recording material thus contains a qualitative high quality color acena image recording and silver tone recording, with the silver tone recording of the developed and processed recording material easily and is obtained without using a separate treatment bath to produce the soundtrack.

The following examples are intended to explain the invention in more detail. example 1

Strips of photographic recording materials, which consist of a transparent layer support made of a gelulose acetate

209829/0957

film and a single gelatin-silver chlorobromide (80/20) emulsion layer applied to it, with 2.15 g (200 mg /
sq.ft.) Gelatin was omitted, and silver was present in the form of silver halide with an average grain size of about 0.1 micron and also the ΒΙΕ-couplers and competing couplers listed in Table IB below,
were exposed to a step exposure object and then,
processed as listed in the following Table IA:

Color development TABLE IA 24 2 5 26 ,? ⁰ O Sec Stop-fix 1 9 ⁰ O Min. 20th Procedure No. treatment 38 ⁰ C Min. 2 Treatment temperature To wash 90 sec. 2 2 Min. 1. Bleach-fix 2 Min. 1 Min. Sec 2. To wash 40 sec. 2 Min. 6th Min. 30th Stabilize 60 sec. 6th Min. Min. Sec 3. 40 sec. 10 Min. 10 4th 80 sec. Sec. 5. 10 sec. 6th

The treatment baths used had the following chemical composition:

1. Color developer

Sodium hexametaphosphate 2 g

Sodium sulfite, anhydrous 4 g

2-amino-5-cLiethylaminotoluene

monohydrochloride 3 g

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Sodium carbonate, monohydrate potassium bromide

topped up with water

2. Stop-fix bath

Sodium thio sulfate Sodium sulfite, anhydrous acetic acid, 28% Boric acid, crystals of potassium alum

topped up with water

21S3576 20th G 2 G 1 liter (pH 10.65) 240 G 15th G 48 ml 7.5 G 15th G Λ liter

Bleach-fix bath

Ethylenediaminetetraacetic acid, Sodium iron salt

Sodium sulfite

Ammonium thiosulfate, 60 / fig solution Ethylenediaminetetraacetic acid, tetrasodium salt

Ammonium thiocyanate topped up with water

6. Stabilizing bath

Formaldehyde (37% by weight solution) Octylphenoxypolyätlioxyäthanol (known under the name "Iriton X-100")

topped up with water

60 G 12th G 200 ml 6.7 G 12th G 1 liter (pH 6.8) 20th ml 2 ml 1 liter

Comparison tests were carried out to determine the percentage of silver that remains when the Process steps 4 (bleach-fix) and 5 (washing) are omitted will. The comparative samples obtained in this way

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contain only developed silver, as the remaining silver halide was fixed out.

The silver density measurements were made on a densitometer at 900 nm and the silver density of the comparative sample was divided into the silver density of the strip which was bleach-fixed by the percentage content in this way to determine the retained silver. The results obtained are shown in Table 1B below.

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sample BJfi coupler mg / m
O (mg / sq.ft _e ) TABLE IB 807 (75) Silver as
Silver halo
genius Procedure back I. 1 140 (13) Competing
Coupler 807 (75) 2
mg / m
(mg / sq.ft.) wise no.
( ⁰ O) hold
Silver % I.
Ch 2 A. 129 (12) 2
mg / m
ö? yp (2) (mp: / sq _e ft.) 807 (75) 666 (62) 1 (38) 100 _Λ
1 3 B. 129 (12) G 807 (75) 807 (75) 2 (24) 100 I. B. 129 (12) G 1150 (107) 807 (75) 3 (26.5) 100 5 B. 129 (12) G 807 (75) 807 (75) 1 100 6th B. 129 (12) (see 807 (75) 786 (73) 1 100 CSD
«S> 7th G 129 (12) E. 1045 (97) 786 (73) 1 100 · ■ 8 C. 129 (12) G 1150 (107) 753 (70) 1 100 9 G 129 (12) J 807 (75) 721 (67) 1 100 S- 10 G 129 (12) K 1045 (97) 721 (67) 1 100 11 G 129 (12) H 807 (75) 743 (69) 1 100 K) 12th D. 129 (12) L. 807 (75) 721 (67) 1 100 CD
CO
cn 13th D. 140 (13) K 1150 (107) 786 (73) 1 100 14th 1 140 (13) L. 807 (75) 721 (67) 1 100 15th I. 323 (30) G 721 (67) 1 100 If H 786 (73) 1 100 G

Footnotes to Table IBs

¹ ΒΙΕ coupler

A. 1 -hydroxy-4 - / "" 1 - (3-undecanamidophenyl) -tetrazol-5-ylthio_7-N- ( 2-n-t e trad "ecyloxyphenyl) -2-naphthamide

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

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

D. i-Hydroxy - ^ - ^ - nonanamido-i, 3,4 - thiadiazol-2-ylthio) -2- / δ - (2,4-di-tert-amylphenoxy) -n-butyl_7-naphthamide

E. 1 -hydroxy-4- / ~ 5- (3,5,5-trimethylh.exanamido) -1,3 »^ - thiadiazol-2-ylthio / -N- (2-n-tetradecyloxyphenyl) -2- naphthamide

P. cc - (Pivalyl) - «i - (5-nonanamido-1,3» 4-thiadiazol-2-ylthio) -2-cnloro-5- / Y -C2,4-di-tert-amylphenoxy) -butyramido_7-acetanIII

ο
Competing matchmakers

G. 1-Hydroxy-N- (2-n-tetradecyloxyphenyl) -2-naphthamia

H. 1- (2,4,6-Trichlorophenyl) -3-t 3- / Ύ - (2,4-di-tert-amylphenoxy) -acetamido_7-benzamido} -5-pyrazolone

J. 1-Hydroxy-2- / Ä - (2,4-di-tert-amylphenoxy) -n-butyl_7-naphthamide "~

K. 1- (6-chloro-2,4-dimethylphenyl) -3- / 5: - (m-pentadecylphenoxy) -butyraiaido_7-5-pyrazolone

L. 1- (2, ^ ₁ 6-Trich.lorophenyl) -3-pentadecyl-5-pyrazolone

The results show that enough lead inhibitor is released imagewise during development to area of the seed developed silver during lead fixation of the recording material

209829/0117

When the indicated gelatin-silver halide emulsion layer was applied as an auxiliary splint on a multilayer color photographic Recording material with three more sensitive color-forming ones intended for the recording of scenes Gelatin-silver halide emulsion units, and exposing the resulting recording material to a color scene image recording, without exposing the auxiliary layer, and also one When exposed to sound recordings and then processed as indicated, color scene image recordings were made from Dye passed and practically free of silver, as well as an excellent sound record made of silver, obtain.

Example 2

Strips of a single layer photographic material of the type identified in Example 1 as Film Sample No. 2 Type were exposed to a step exposure object, whereupon, as described in Table II below, at 30 ° C processed. The numbers given in Table II mean time in seconds, unless stated otherwise.

TABLE II Procedure No. 1 2 3 4- 5

1. Gate bath treatment

2. Washing

3. Color development 4-, washing

5. Stop treatment

'6. Stop-fixing treatment

7. Washing

8. Bleach-fix

9. Washing 120 120 120 120 120

209329/0957

10 10 10 10 10 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

10. Stabilize 10 10 10 10 10

restrained

Silver density - 100 % 100% 88% 71%

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

' 1st pre-bath

Borax sodium sulfate, anhydrous sodium hydroxide, 10% solution made up to pH value with water

5. Stop bath

Glacial acetic acid sodium bisulfite made up to pH value with water

8. Bieichfixierbad (always used except in procedure no. 3.

Hydrochloric acid sodium sulfite ammonium iron-ethylenediaminetetraacetic acid (1.56 molar solution) ammonium thiosulfate (60% solution) made up with water PH value

20th , 3 S. , 76 , 2 ml 100 , 5 S. Procedure ¹ G 10 ml 9 ml 1 liter 12th ml 9 92 liter 24 ml 200 , 5 6th G 1 1 liter 6th 3

209829/0957

7th δ 20th S. 200 ml 4th 6th Λ liter

-65-2163578

8. Bleach-fix bath (for procedure # 3)

Ethylenediaminetetraacetic acid,

Sodium iron salt 60 g

Ethylenediaminetetraacetic acid, tetrasodium sal

Sodium sulfite

Ammonium thiοsulphate (60% solution)

Potassium iodide

topped up with water

pH 6.8

The recording material processed according to Procedure No. 1 was fixed but not bleach-fixed. Since this recording material was not bleached, it therefore contains 100 % of the developed silver and is used as a reference value for determining the effectiveness of the bleach inhibitor in retaining the silver during the bleach-fixing. The percentage of silver retained was determined according to the procedure described in Example 1.

The results obtained show that the retained SiI over density in all cases is large enough to make a high quality silver tone track.

Has it been specified ?! Gelatin silver halide emulsion layer applied as an auxiliary layer to a multi-layer color photographic recording material with three more highly sensitive, color-forming Gelatin® silver halide emulsion units ₉ and the srhalt® recording material a © ißhnuns © impressed, o! »j dl © 3iX * 3.fi? Mofet * WM " feaXi © ^ to2i ₅ s © ui® Qtnes Sonauf aaieteußg qss-

woiscss iWo Z Ms p WäPs ^ Tfeciitots, θ ©

fooi

Were silver, as well as excellent sound recording that consisted of silver.

Example 3

Three multilayer color photographic recording materials were tested with scene recording and sound recording districts, each of which has three color-forming units capable of scene recording, each of which is opposite was sensitive to another primary color region of the visible spectrum, as well as one capable of sound recording Auxiliary layer of the composition given below, the was sensitive to the blue region of the visible spectrum.

The recording materials to be tested were color scene image negatives exposed to white light, as well as a sound recording negative exposed through a filter pack containing a narrow band of light with one peak at 470 nm and one Bandwidth of 20 nm at half transmission lets through, whereupon the exposed recording materials according to the procedure No. 2 of Example 2 were processed.

The composition of the recording materials used are given below. The approximate amount of

those components, expressed in mg / m, are in parentheses specified.

Recording material I

On a transparent support made from a cellular acetate film the following layers were applied to one side in the following order:

<1) a blue sensitive, capable of scanning image recording-

208828/0967

te, color-forming photographic unit made of gelatine (3650), silver (64-5) in the form of silver bromoiodide, with 1 % iodide, a non-diffusible, open-chain ketomethylene coupler capable of forming yellow dyes (1400) and dibutyl phthalate as a coupler solvent (1400) ,

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

(5) a red-sensitive color-forming photographic unit capable of recording scenes, consisting of gelatin (3000), silver (430) in the form of silver chlorobromide with 20 % bromide, a non-diffusible phenolic photographic coupler (810) capable of forming cyan dyes and dibutyl phthalate as Coupler solvent (2420),

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

(5) a green-sensitive, capable of scene recording, color-forming photographic unit made of gelatine (2360), silver (860) in the form of silver chlorobromide with 20% bromide, a nondiffusible 5-pyrazolone photographic coupler capable of forming magenta dyes (1450) and tricresyl phosphate (700) as coupler solvents,

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

(7) one capable of sound recording, opposite the blue one Sensitive auxiliary layer in the visible spectrum made of gelatine (1600), silver (750) in the form of silver

20982S / 0857

robromide with 20 % bromide, with an average grain size of about 0.1 micron, BIR coupler A of Example 1 (140), Coupler G of Example 1 (810), 2,5-dioctylhydroquinone (81) and tricresyl phosphate (485) as a coupler solvent, as well

(8) a top layer of gelatin (970). Recording material II

On a transparent cellulose acetate film support the following layers were applied to a surface in the following order:

(1) a blue-sensitive, color-forming photographic unit capable of recording scenes, made of gelatine (3650), silver (645) in the form of silver bromoiodide with 1 % iodide, a non-diffusible, photographic open-chain ketomethylene coupler (1400) and dibutyl phthalate capable of forming yellow dyes (1400) as a coupler solvent,

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

(3) a red-sensitive color-forming photographic unit capable of recording scenes from gelatine (3000), silver (430) in the form of silver chlorobromide with 20 % bromide, a non-diffusible phenolic coupler capable of forming blue-green dyes (810) and dibutyl phthalate ( 2420) as a coupler solvent,

(4) one for sound recording opposite the blue area of the visible spectrum sensitive auxiliary layer made of gelatin

209829 / 0Θ57

tine (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 of example 1 (140), the coupler G of example 1 (810), 2,5-dioctylhydroquinone (81) and tricresyl phosphate (485) as coupler solvents,

(5) a green-sensitive color-forming photographic unit made of gelatine (2360), silver (860) in the form of silver chlorobromide with 20 % bromide, a non-diffusible 5-fyrazolone coupler capable of forming purple dyes (1450) and capable of forming scenes Tricresyl phosphate (700) as a coupler solvent, as well as

(6) a top layer of gelatin (970). Recording material III

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

(1) a blue-sensitive, color-forming photographic unit capable of recording scenes, made of gelatin (365O) ₁ silver (645) in the form of silver bromoiodide with 1% iodide, a non-diffusible photographic open-chain ketomethylene coupler (1400) and dibutyl phthalate which is openly capable of forming oil-colored open-chain couplers (1400) they coupling agent,

(2) an interlayer sue gelatiao (64-5) hydroquinone (31),

(?) “I am qualified to die, gsittber dee blue Btreieh & · «edible sisktpisias © apf iadlieli © help

of gelatine (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 of example 1 (140), the coupler G of example 1 (810 ) 2,5-dioctylhydroquinone (81) and tricresyl phosphate (485) as coupler solvents,

(4) a red-sensitive, color-forming photographic unit made of gelatine (3000), silver (430) and capable of producing scenes in the form of SiIb er chi or obromid with 20 % bromide, a non-diffusible phenolic photographic unit capable of forming blue-green dyes Coupler, (810) and dibutyl phthalate (2420) as coupler solvents,

(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 nondiffusible 5-pyrazolone coupler capable of forming purple dyes (1450 ) and tricresyl phosphate (700) as coupler solvents, as well

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

The developed films contained yellow, purple, and cyan dye image records that were essentially free of Silver were as well as excellent silver tone records. When the finished films were projected with the aid of an optical sound projector, excellent image and Receive sound recordings.

203329/0357

Example 4

Consisting of strips of photographic recording materials from a transparent support made from a cellulose acetate film and coated thereon a single layer of a fogged direct positive gelatin-silver halide emulsion layer of the type described in French patent 1 520 821, with a content of silver in the form of silver halide, and of the BIR couplers and competing ones listed in Table IV-B below Couplers, were exposed to a step exposure object and then processed as in the following table IV-A described:

TABLE IV-A 30th Sec. 1 Min 1. Black and white development 30th Sec. 2. Stop bath H- Min 3. Washing 1 Min 4-, reverse flash exposure 1 Min 5. Color development 1 Min 6. Vaschen 7. Bleach-fix 8. Vaschen 10 Sec. 9. Stabilize 52 ⁰ C Treatment temperature

The chemical composition of the treatment baths used was as follows:

209829/0957

1. Black and white developer H ₂ SO ₄

Sodium sulfite

• 4-1-phenyl-5-pyrazolidone

K ₀ CO,

Hydroquinone NaBr

1.8 ml 25th G 0.6 G 16.0 S. 8.0 S. 1.5 S. 12.0 S. 7th mg 12.0 cc 1 liter 9.9 800 ml 27 ml 8.7 S. 1 liter

KJ

Diethylene glycol made up to pH value with water

2. Abetop bath

Water glacial acetic acid NaHSO _{3 made up} with water

5. Color developer

Sodium sulfite 2.5 g

4-amino-5-methyl- (N-ethyl-N-

methoxyethyl) aniline-1,5-naphthalene,

Disulfonic acid (color developing agent)

K ₀ CO, 2 5

NaBr KJ

Citrazinic acid KOH (45% solution) 5,6-dithiaoctane-i, 8-thiol topped up with water

pH 10.7

14.0 G G 56.0 S. ml , 5 G G , 028g liter 1.0 5.0 1.0 1

2-09829 / 0957

7 »Bleach-fix solution

Sodium Iron EDTA Sodium Sulphite

Ammonium thiocyanate ammonium thio sulfate (60% solution) Tetrasodium EDTA

made up to pH value with water

9. Stabilizing bath

wt, formaldehyde (37% solution) 20 ml

Octylphenoxy-polyethoxyethanol (known as ¹¹ Triten X-100 ") 2 ml

made up to 1 liter with water

The composition of the film samples used is shown in Table IV-B below.

60.0 S. 12.0 G 12.0 S. 200 ml 6.7 6th 1 liter 6.68

209829/0967

Movie
sample
Mr. gelatin (mg / sq.ft .; ) 0 mg / m TABEL BIR IV-B Competition 806 . Coupler Silver as
Silver halide
mg / m (mg / sq.ft.) (7D I.
-p? 1 2
mg / m (200) A. _ Coupler ² (mfc / sq.ft.) 2 806 (mR / sq.ft.) 763 (7D I. 2 2150 (200) C. 333 806 (75) '763 (79) 3 2150 (200) 269 (30) G (75) 850 κ »
O 2150 (25) G (75) (O
SD G (O SO
cn

(a) Coupler Nos. A, 0 and G are explained in the footnote of Table 1-3.

The silver densities obtained were measured on a densitometer at 900 nm measured. The results obtained are as follows Listed in Table IV-C.

TABEL IV-C developed Max. E ^(b) held back "Max. _E (b) Silver density Min. E < ^b > 0.96
0.96
1.02 Min. E ^(b) 0,
0,
0, 06
86
84 Movie 1.40
1.42
1.58 0.05
0.05
0.04 sample
No. 1
2
3

^ 'Min. E = minimum exposure; Max. E = maximum exposure.

The results show that enough during development Bleach inhibitor is imagewise released to a substantial proportion of the developed silver during the bleach-fix to keep the film sample. The silver retained during the bleach-fix was negative Image and not a normal positive image that would be obtained if the auxiliary layer had a negative, developable image Silver halide would be present and the recording material would be reverse processed in exactly the same way as the specified photographic material On drawing materials.

If the indicated gelatin-silver halide emulsion layers were applied as an auxiliary layer on a multilayer color photographic reversal film with three higher sensitivity usual known, capable of scene recording, gelatin-silver halide color-forming emulsion units arranged and sensitized in such a manner that each

209829/0957

of them is practically sensitive to another primary color region of the visible spectrum, and where the auxiliary layer due to its particular sensitivity to radiation in the imagewise exposure of the scene image recording units no image was formed, and the resulting recording materials became a color scene image recording exposed without the auxiliary layer being exposed and exposed to a sound recording, and the exposed ones were exposed Recording materials as described in Table IV-A, processed, color scene image recordings were made obtained made of dye and practically free of silver, as well as excellent negative sound recordings, that were made of silver.

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. 7 capable of sound recording consisted of gelatin (1500), gilber (54-0) as silver chlorobromide with 20 mol% Bromide and an average grain size of about 0.1 micron, the BIR coupler 1-hydroxy-4- / ~ 1- (3-undecanamidophen7 / l) -tetrazol-5-ylthio_7-N- (2-n-tetradecyloxyphenyl) - 2-naphthemid (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-ethyl5- (3-ethyl-2 -benzothiazolinylidene) -rhodanine (150 mg / mol silver), which gives a maximum sensitization at about 480 nm, was achieved by a step wedge with a scene exposure with white light, as well as with a soundtrack exposure with light of a narrow bandwidth, the intensity of which is 4-70 nm lay, see n, whereupon the exposed recording material was processed as follows:

209829/0957

1st pre-bath treatment 10 sec.

2nd wash 10 sec.

3rd color development 90 sec. 4-, washing 10 sec.

5. Stop-fixing treatment 60 sec.

6. Wash 30 sec.

7. Bleach-fix 60 sec.

8.Wash 120 sec.

9. Stabilize 10 sec. Treatment temperature 38 G

Treatment baths 3, 5 and 9 had the same composition as baths 1, 2 and 6, respectively, of Example 1. That used Pre-bath had the same composition as that in Example 2 used, and the bleach-fix bath used had the same composition as the bath used to carry out Procedures 2, 4 and 5 of Example 2. The cross-modulation density of the recording material obtained was within the range corresponding to one usable sound volume and good film durability.

Was exposed to the specified recording medium a multi-color image recording scene and an audio track, then developed as indicated, and after completion projected by an optical Tonprojektors _t so wurdaebei subjective evaluation obtained by observing persons excellent images and sounds.

Example 6

To produce a comparative film, a layer support " made of collulose triseotate © in © Gelatin © = silver chlorobromide emulsion, d © p © & Ealogeiiidkompoa®nfce to 80 mol%

ρ consisted of Ohlorid, in dor 'Weiss that per m

Φ · ρ »Η0 ·« τ »· Ρ1 Hph ■■»

(400 mg / sq.ft.) Gelatine were omitted, and furthermore per m Support area 0.86 g (80 mg / sq.ft.) Of competing photograph Coupler 1-hydroxy-2- / Ä - (2,4-di-tert-amylphenoxy) -n-butyl_7naphthamide, dissolved in about 1.3 g / m (120 mg / sq.ft.) of the coupler solvent, di-n-butyl phthalate.

A test film sample was prepared in the manner indicated,

2, however, with the exception that, in addition, per m of support area • 0.43 g (40 mg / sq.ft.) Of the bleach inhibitor-releasing hydrquinone compound 2,3-Dimethyl-5- / ~ 1- (3-nonanamidophenyl) -tetrazolyl-5-ylthio_7hydroquinone were incorporated.

The two film samples were exposed and processed as described in Example 1. The results obtained showed that in the test film sample after the bleach-fixing, a sufficient one Amount of silver was retained to make a usable soundtrack, whereas in the comparative sample no significant amount of silver had been held back.

Similar results were obtained when the specified procedure, but replacing the color developer compound used with a black and white developer compound of the type described in Example 4.

Correspondingly advantageous results as in Example 3 were

there
contact repetition of / given procedure but de substituting "-eBIH-KupplersA · used the recording materials specified I _s II and III, by the used in the present example BIR hydroquinone compound.

209829/096?

Claims (17)

Patent to speak 1.- Photographic process for the production of scenes and silver tone track type auxiliary pictures in one and the same Recording material in which a photographic recording material consisting of a layer support, at least one applied thereon for scene image recording capable, color-forming photographic unit having at least one silver halide emulsion layer as well as, if necessary, intermediate and / or top layers, exposed, developed into silver-containing scenes and auxiliary images and, after protection of the silver developed in the silver auxiliary image district against fading, for the removal of the scene image syllable ^? and remaining silver halide bleached and fixed is, characterized in that a photographic recording material is exposed, which in addition to a Auxiliary silver image recording enabled silver halide emulsion layer has such a radiation sensitivity that in the imagewise exposure of the scene image recording unit no image is generated in it, as well as with a content of a non-diffusible, self-releasing weight inhibitor Compound which, when reacted with oxidized developer compounds, acts as a lead inhibitor, at least one thiol or selenol carrying a hydrophobic radical as a ballast group, and that one in the Scene image on the recording unit of the exposed recording material an image consisting of dye and silver is generated and in the auxiliary layer of the exposed recording material the silver halide reacts with a photographic developing agent to produce one Silver image and oxidized photographic developing agent before bleaching and fixing. 209328/0957 2. Multilayer color photographic recording material for carrying out the method according to claim 1, consisting of a layer support, three applied to it, for Color-forming photographic recordings capable of scene recording Units each having at least one silver halide emulsion layer, which are arranged and sensitized in such a way that each unit is practically opposite Sensitive to another primary color region of the visible spectrum and for recording practically blue, green or red light is capable, and optionally intermediate and / or top layers, characterized in that the . Recording material additionally one for auxiliary silver image recording capable silver halide emulsion layer with such radiation sensitivity that at the imagewise exposure of the scene image on recording units no image is produced in it, as well as containing a non-diffusible, bleach inhibitor-releasing one Compound which, when reacted with oxidized developer compounds, acts as a silver bleach inhibitor, forms at least one thiol or selenol bearing a hydrophobic residue as a ballast group. 3. Recording material according to claim 2, characterized in that the silver halide present in the auxiliary layer has an average grain size of 0.05 to 0.5 microns. 4. Recording material according to Claims 2 and 3, characterized in that 2 indicates that in the auxiliary layer per m of carrier area 0.215 to 1.62 g (20 to 150 mg / sq.ft.) Of silver in the form of Silver halide are present. 5. Recording material according to Claims 2 to 4, characterized in that that the auxiliary layer additionally contains a scavenger for oxidized color developing agent, the 209829/0957 reacts with oxidized color developing agent at about the same rate as the one that releases the bleach inhibitor Link. 6. Recording material according to claims 2 "to 5» characterized in that that the bleach inhibitor releasing compound consists of a bleach inhibitor releasing hydroquinone consists. 7. Recording material according to claims 2 to 5, characterized in that the bleach inhibitor-releasing compound consists of a bleach inhibitor-releasing coupler, one component of which is a photographic color coupler which is substituted in the coupling position with the bleach inhibitor component which is attached to the color coupler via the Sulfur or selenium atom of the thiol or selenol group present in it is bonded and consists of the remainder of a mercapto- or selenol-substituted alkanoic acid, an aryl thiol or selenol, a heterocyclic thiol or selenol, a thiocarboxylic acid or a thiocarboxylic acid ester, a mercapto or has a molecular weight of at least 125 regardless of the selenol group, and contains at least one ballast group in the form of a hydrophobic radical which controls the diffusion rate of the bleach inhibitor compound into a hydrophilic colloid layer . 8. Recording material according to claim 7, characterized in that the bleach inhibitor-releasing coupler consists of a compound of the following formula SRC in which meanι KUP the best of a photo-graphic coupler «the in «A coupling position is substituted with the 200628/0867 Radical of the formula - X (ΑΧ a sulfur or selenium atom, 1 1
the grouping - (- A-) H is an organic component, the. "together with the Best X is a ballasted group as silver bleach inhibitor acting compound when the coupler reacts with an oxidized I ¹ arbentwickle rverbiindung aromatic primary amine type, a ■ O, 1, 2, 3i * i 5 or 6, R is a halogen atom, or a nitro, alkyl or aryl radical or a thio radical with 3 to 22 carbon atoms, an amido radical with 4 to 22 carbon atoms or a carbonyl, orarbamoyl, alkoxy or aryloxy radical, and A is a carbonyl, thiocarbonyl or carboxymethylene radical, or a 3- to 6-membered carbocyclic Ring or a 3- to 10-membered heterocyclic Ring with at least one carbon and at least one nitrogen, oxygen, sulfur or selenium atom, where R is not a carbonyl, carbamoyl or amido radical indicates when A represents a carbonyl or thiocarbonyl radical, and 1 1
where the grouping R '(Al -) - has a component a »molecular weight of 125 to 1000 and furthermore, when A is a carbocyclic or a heterocyclic Ring means, this carbocyclic or heterocyclic ring with a hydrophobic radical subetitu- is ied. 9. Recording material according to claim 8, characterized in 1 A
net that the group R - A is a benzoxazole, benzo thiazole, benzimidazole, thisdiazole, triazole or 1-phenyltetrazole radical means. 10. Recording material according to claims 7 and 8, characterized in that that the bleach inhibitor releasing coupler consists of a compound of one of the following formulas: (a) (R ^ -C-F) - 1 Il. N s-SRC 10
where η = * 1, 2, 3, 4 or 5 »R is an alkyl radical having 1 to 17 carbon atoms and KUP is the radical of a photographic coupler substituted in the coupling position by the specified thio radical; (b) (R ^IJ CN) - I ^X > - S KUP in which η «1, 2, 3, 4 or 5, R denotes an alkyl radical having 1 to 17 carbon atoms and KUP denotes the radical of a photographic coupler substituted in the coupling position by the specified thio radical; 209829/0957 12th
in which η - 1, 2, 3, 4 or 5, R is an alkyl radical having 1 "to 17 carbon atoms and KUP is the radical of a photographic coupler substituted in the coupling position by the specified thio radical; N N (a) r ¹ ^ --ζ - σ c - s - κυρ wherein Z is a sulfur atom or a radical of the formula -NHCO-, 1 ^
R ^ is an alkyl radical having 5 to 17 carbon atoms and KUP denotes the radical of a photographic coupler substituted in the coupling position by the specified thio radical; 0 Yy N - S. -KUP Il Il Il C - N— -C C. (β) R 14th
wherein R is an alkyl radical having 5 to 17 carbon atoms and KUP the remainder of one in the coupling position by the specified Thio radical substituted photographic coupler; 209829/0957 SRC HN Ή where η »1, 2, 3, * or 5, E is an alkyl radical with 1 to 17 carbon atoms and SRC the best one in coupling Position by the indicated thio radical substituted photographic coupler mean. 11. Recording material according to Claims 7 and 8, characterized in that that the bleach inhibitor releasing coupler is composed of 1-hydroxy-4- (5-nonanamido-1,3-benzimidazol-2-ylthio) -N- (2-n-tetradecyloxyphenyl) -2-naphthamide consists. 12. Recording material according to claims 2 to 11, characterized in that the auxiliary silver image is a silver-tone track recording. 13. Photographic recording material according to claims 2 to 12, characterized in that several color-forming units are present and these have minimal sensitization to at least one region of the spectrum which bridges adjacent sensitized color-forming units , and that the auxiliary layer sensitizes to such an area of minimal sensitization and has a photographic speed at least 2 times less than the photographic speed of the color-forming units of adjacent spectral sensitization when selectively exposed in the region of minimal sensitization. 30II2I / QII7 14. Recording material according to claim 13, characterized in that the auxiliary ssilberbild the auxiliary sschicht from consists of a silver-tone track recording. 15 · Recording material according to claims 13 and 14, characterized characterized in that there are (1) one for scene image recording capable color-forming photographic unit comprising at least one silver halide emulsion layer which is primarily sensitive to the blue region of the visible spectrum and is non-diffusible contains photographic couplers capable of reacting with oxidized I color developing agents of the primary aromatic Amine type is capable of forming a nondiffusible yellow dye, (2) one for scene recording capable color-forming photographic unit with at least one silver halide emulsion layer, which is primarily sensitive to the red region of the visible spectrum and is non-diffusible contains photographic couplers which react with oxidized I-carb developing agents from the primary aromatic amine type is capable of forming a nondiffusible cyan dye, and (3) one color-forming photographic images capable of recording scenes Unit with at least one silver halide emulsion layer primarily opposite the green area of the visible spectrum is sensitive and nondiffusible contains photographic coupler which reacts with oxidized color developing agents is of the primary aromatic amine type capable of forming a nondiffusible purple dye, and that the color-forming units have minimal sensitization at least with respect to the region of the spectrum containing the blue- and green-sensitive color-forming units bridged, have, and d * ß these blue- and green-sensitive color-forming units a 2 to 15-fold 209829/0957 higher photographic sensitivity than the auxiliary layer own when in the area of minimal awareness is exposed. 16. Recording material according to claims 13 and 14, characterized in that there are (1) one for recording scene images capable, color-forming photographic unit comprising at least one silver halide emulsion layer which is primarily sensitive to the blue region of the visible spectrum and is non-diffusible contains photographic coupler which reacts with oxidized color developing agents of the primary aromatic Amine type with the formation of a non-diffusible one Yellow dye is capable of (2) a scene image recording capable, color-forming photographic unit having at least one silver halide emulsion layer primarily facing the red region of the visible spectrum is sensitive and contains a nondiffusible photographic coupler capable of reacting with oxidized primary aromatic amine type color developing agents to form a nondiffusible one Cyan dye, and (3) one for scene recording capable, color-forming photographic unit with at least one silver halide emulsion layer, which is primarily sensitive to the green region of the visible spectrum and which is nondiffusible contains photographic coupler, the reaction with oxidized color developing agent from primary aromatic amine type is capable of forming a nondiffusible purple dye, and that the color-forming units have minimal sensitization at least to the region of the spectrum which the red- and green-sensitive color-forming units bridged, and that the red- and green-sensitive Units are 2 to 15 times higher photographic Have sensitivity as the auxiliary layer when exposed in the area of minimal sensitization. 17. Recording material according to claim I5 »characterized in that that the auxiliary layer has minimal sensitization with the aid of 5-ethyl-5- (5-ethyl-2-benzothiazolinylidene) rhodanine compared to the specified range is sensitized. 209829/0957