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Publication numberUS3705799 A
Publication typeGrant
Publication dateDec 12, 1972
Filing dateDec 17, 1971
Priority dateDec 17, 1971
Publication numberUS 3705799 A, US 3705799A, US-A-3705799, US3705799 A, US3705799A
InventorsHobson J Bello, Carl F Holtz
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Film and process using bleach inhibitor for producing color film with silver sound record
US 3705799 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Dec. 12, 1972 H. J. BELLO ETAL FILM AND PROCESS US COLOR FILM Fi BLUE WHITE LIGHT EXPOSURE 3,705,799 ING BLEACH INHIBITOR FOR PRODUCING WITH SILVER SOUND RECORD led Dec. 17, L971 GREEN LIGHT EXPOSURE I MA GE d-SUPPOR T ORIGINAL smaE I, I, I

BLUE-GREEN SENSITIVE, MAGENTA FORMING AUXILIARY LAYER t-GREEN SENSITIVE, MAGENTA FORMING LAYER 'RED SENSITIVE, CYAN FORMING LAYER -BLUE SENSITIVE, YELLOW FORMING LAYER SUPPORT F- SOUND TRACK RECORD, SILVER 8 MAGENTA IMAGE GREEN RECORD, SILVER 8 MAGENTA IMAGE RED RECORD, SILVERBCYAN IMAGE BLUE RECORD, SILVER 8 YELLOW IMAGE SUPPORT SIAGE 3 SOUND TRA CK RECORD PROTECTED B Y BLEACH INHIB/ TOR GREEN RECORD PART/ALLY PROTECTED BY BL EACH INHIBITOR RED RECORD BLUE RECORD SUPP OR T S7AGE 4 SOUND TRACK RECORD, MAGENTA DYE 8 28 2/0 +29 27 27 SILVER IMAGE GREENRECORD, MAGENTA DYE IMAGE, SILVER SOUND RECORD RED RECORD, CYAN DYE IMAGE BLUE RECORD, YELLOW DYE IMAGE HOBSON J. BELLO CARL E HOLTZ INVENTORS BY gm Q .5

A TTORNE Y SUPPORT 3,705,799 FILM AND PROCESS USING BLEACH INHIBITOR FOR PRODUCING COLOR FILM WITH SILVER SOUND RECORD Hobson J. Bello and Carl F. Holtz, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N .Y. Continuation-impart of abandoned application Ser. No. 100,609, Dec. 22, 1970. This application Dec. 17, 1971, Ser. No. 209,362

Int. Cl. G03c 5/44, 7/24 US. Cl. 96-4 49 Claims ABSTRACT OF THE DISCLOSURE A novel process of producing a picture record and a silver auxiliary or sound record in an imagewise exposed photographic element comprising a support having coated thereon, on one surface in order from the support, a picture recording photographic image-forming unit comprising silver halide layers and an auxiliary image recording radiation sensitive silver halide layer which does not form an image upon image-forming exposure of the picture recording unit is provided which comprises (A) developing a picture record comprising silver and a nondilfusible dye and an auxiliary image or sound record comprising silver, (B) contacting the auxiliary layer with a ballasted silver bleach inhibitor to adsorb the bleach inhibitor onto at least the silver of the auxiliary image or sound record and (C) removing the bleachable silver images and residual silver halide. Also provided are novel photographic elements similar to the type described above having a plurality of picture recording image-forming units an an auxiliary layer containing a colorless nondiftusible compound which reacts with aromatic primary amine color developing agent and which decreases the rate of diffusion of a ballasted silver bleach inhibitor through the auxiliary layer.

This application is a continuation-in-part of our copending US. patent application Ser. No. 100,609 filed Dec. 22, 1970 and now abandoned.

This invention relates to color photographic films having an auxiliary metallic silver image. In one aspect, this invention relates to color motion picture films having metallic silver sound tracks and more particularly to color photographic films, compositions and processes useful in preparing such motion picture films.

Color photographic films having auxiliary metallic silver images are known. Color motion picture films having silver sound tracks are well known. Typically, the color images are prepared by the three-color system of photo-graphy. In this well known system color images are formed from three subtractive dyes: a yellow dye to control blue light, a magneta dye to control green light and a cyan dye to control red light. These dye images can be formed by various methods.

For example, color images can be produced by the dyebleach process. This process uses a film which has incorporated therein, in three separate layers, each sensitive to a primary color region of the visible spectrum, a preformed subtractive dye which is capable of being destroyed in proportion to the silver formed upon developmentof a latent photographic image.

Another method of preparing a three-color record by the subtractive dye process is to photographically record an image in a photographic element having three photographic silver halide layers in a superposed relationship to each other, each layer being sensitive to essentially one primary color region of the visible spectrum. These photographic silver halide layers can contain photographic color couplers which form, upon coupling with oxidized United States Patent 0 aromatic primary amine color developing agent, subtractive dyes essentially complementary to the primary color regions of the visible spectrum. These photographic silver halide layers can, alternatively, not contain photographic color formers; the color image then being produced by processing in a coupler-developer composition to form nondilfusible subtractive dyes. Subsequent to dye image formation, the developed silver and the residual silver halide must be removed from the picture area. This is usually accomplished by bleaching and fixing or by bleachfixing (single step bleaching and fixing).

Optical motion picture sound tracks are printed onto the same film on which the picture image was printed. Optical sound tracks can be of the variable density or variable area types. The sound track itself can be comprised of dyes, dyes plus silver, silver compounds, silver plus other metals or silver alone. The photocell used almost universally to detect light passing through an optical sound track is of such nature that it is most sensitive to electromagnetic radiation of a wavelength greater than 700 nanometers (nm.) with a peak sensitivity at about 800 nm. The subtractive dyes which form the picture image have regions of maximum absorption from 400 to 700 nm. Consequently, these dyes are nearly transparent to infrared radiation and have very little modulating effect upon this radiation to which the photocell is most sensitive.

Silver produced as a result of the chemical reduction of a latent silver halide image is uniformly opaque to the full spectrum of radiation ranging from ultraviolet through visible into the infrared region and acts as an excellent modulator for infrared radiation to which currently used optical photocells are most sensitive. Silver compounds such as silver sulfide and silver toned with metals such as gold are also more opaque than image dyes to infrared radiation. It can thus be seen it is preferable that optical sound records in color motion picture films be comprised of substances other than subtractive image dyes. The presence of subtractive dyes in addition to the other substances, however, is not objectionable.

As noted above, the developed silver and the residual silver halide must be removed from the picture area of a color motion picture film subsequent to color image formation. At the same time developed silver or a silver compound must be retained in the sound track area if the color motion picture film is to have the preferred sound track. A number of techniques have been devised to retain silver in the sound track area of color motion picture films during bleaching and fixing of the silver and residual silver halide in the picture area. For example, the sound track area can be covered with a varnish subsequent to formation of the picture and sound track images and proir to silver and silver halide removal. The varnish prevents diffusion of the bleaching solution into the sound track area. Subsequent to rehalogenation of the silver in the picture area, the varnish is removed with a suitable solvent and silver halide is removed from the entire film, reference being made to US. Pat. 1,973,463, issued Sept. 11, 1934 and US Pat. 2,113,329, issued .Apr. 5, 1938.

A currently used method of retaining metallic silver in the sound track area is to print the picture and sound track images in the photographic silver halide element and develop the latent image to metallic silver. In print films the residual silver halide is removed by fixing the entire film. In reversal films only the sound track area is fixed followed by color reversal development. At this point, both types of film have a sound track of metallic silver free from residual silver halide. The metallic silver is then converted to a fixable silver salt by bleaching both the sound track and picture areas. In the sound track area, the silver salt is reconverted to metallic silver by applying a viscous, highly active developer, for example, by known striping techniques. Subsequently, the silver salt in the picture area is removed by fixing.

Another method of preventing the removal of the silver sound track is to treat the silver metal with a solution which produces a gold tone. This gold-toned silver metal is not removed upon bleaching and fixing, reference being made to U.S. Pat. 2,263,019, issued Nov. 18, 1941.

Still another method is to stripe the sound track area of the film with a quaternary ammonium salt which renders the silver metal unbleachable, reference being made to U.S. Pat. 3,243,295, issued Mar 29, 1966.

Still another method of retaining silver metal in the sound track area is to prepare a photographic multilayer element which forms a dye in the upper layer during chromogenic development which dye is reducible to a leuco dye which can reduce silver ions in solution to silver metal. The developed sound area is striped with water and passed through a sulfur dioxide gas atmosphere where the gas is absorbed only in the moistened sound track area. The absorbed gas reduces the dye to a leuco dye. The film is then passed through an ammonia-silver nitrate solution where the leuco dye reduces silver ions to silver metal which is deposited in the film, reference being made to U.S. Pat. 2,286,747, issued June 16, 1942.

Alternatively, the silver in the sound track area can be converted to compounds or complexes which resist the bleaching of the silver. For example, silver or silver halide can be converted to silver sulfide prior to bleaching. The sulfide is not converted to a fixable silver salt by bleaching and thus remains as silver sulfide following fixing, reference being made to U.S. Pat. 2,143,787, issued Jan. 10, 1939. The treatment solution can contain both sulfiding and iodizing compounds which also convert the silver to a compound which is not removed upon bleaching and fixing, reference being made to U.S. Pat. 2,258,976, issued Oct. 14,1941.

Still another method of preparing a sound track is to coat a separate layer on the back of the film support. Each of the two sides to the film is processed without contacting the other side with the processing solutions, for example, by floating the film on the surface of the solution, reference being made to U.S. Pat. 2,235,033, issued Mar. 18, 1941.

The above techniques refer to only a small number of the patented or known methods or refinements for producing silver or silver complex sound tracks in color motion picture films.

The disadvantage of all methods known today is the requirement of separate treatment of a portion of the film at least once during processing. The method most commonly used today involves the use of a striping device which applies a narrow bead of reagent to the sound track area. In order to use a striping device the film must be taken out of the processing solutions and dried by passing between ringer-type rollers or between squeegees. The film is then passed through the striping device which, in one form, comprises a rotating wheel dipping into a viscous processing solution which is then applied by the wheel in the form of a bead on the edge of the film. The conditions under which this striping process is performed are critical. For example, the striping wheel is only 0.094 inch wide for 16 millimeter film. If the striping wheel picks up an insufiicient amount of process ing composition, too little will be applied to the film and an inferior sound track can result. If the striping wheel picks up too much processing solution, the bead applied to the film will be too wide and can cover part of the picture area. In this event, silver will be retained in the picture area degrading the color image in those areas. Another problem with this type of striping technique is that if the film is vibrated in some manner, the viscous process ng composition can flow into h pi tur area with the same result. Although the striping technique has been refined throughout the years, the conditions under which this process is performed are still so critical that a small amount of error inevitably occurs. Sometimes the error can be corrected by partially reprocessing the film. On other occasions the film is ruined and must be discarded. Whatever the result of error arising from the striping process and even though the amount of film affected by such error amounts to only a fraction of a percent of the film processed, these errors are economically costly.

It has been found that when a developed silver image is contacted with a silver bleach inhibitor subsequent to initial development and prior to bleaching, the silver is rendered unbleachable. Therefore, when only the sound track portion of a film having a silver sound record is contacted with a silver bleach inhibitor this silver sound record is rendered unbleachable. This method is disclosed and claimed in copending application Bevis, Hello and Holtz, entitled Process for Preparing Color Film with Auxiliary or Silver Sound Record Using Bleach Inhibitor, Ser. No. 100,608, filed Dec. 22, 1970, now abandoned, and the continuation-in-part thereof filed concurrently herewith. Although this method of producing sound tracks represents a significant advance over previously known striping methods since, for negative-positive print films, it involves a single application to the sound track area of a solution, the concentration, temperature and contact time of which are not critical, it still requires a separate treatment of the second track area of the film.

Thus, it appears desirable to provide a method by which a silver sound record or auxiliary silver image can be produced in a color photographic film which avoids the separate treatment of any area of the film at any stage of the processing and thus avoids the inherent problems of these various prior techniques. In brief, it is desired to produce a high quality silver sound track by relatively simple processing techniques.

Accordingly, it is an object of our invention to provide a novel method of preparing auxiliary metallic silver images in color films.

It is a further object of our invention to provide a novel method of preparing silver sound tracks in motion picture film.

It is still a further object of our invention to provide a novel method of preparing silver sound tracks in color motion picture films by simple processing techniques.

It is still a further object of our invention to provide silver sound tracks in color motion picture films by novel processing methods which avoid the use of techniques involving individual treatment of separate areas or sides of the photographic element.

It is an object of our invention to provide novel photographic elements for the preparation of auxiliary metallic silver images in color photographic films.

It is a further object of our invention to provide novel photographic elements for the preparation of silver sound tracks.

It is still a. further object of our invention to provide novel photographic elements for the preparation of color motion picture films having silver sound tracks by simple processing techniques.

It is still a further object of our invention to provide novel photographic elements for the preparation of color motion picture films having silver sound tracks by processing methods which avoid individually processing separate areas or sides of the element.

Other objects will become apparent from the following specification and the appended claims.

Our novel method of processing photographic elements having imagewise exposed picture areas and imagewise exposed sound track areas or auxiliary images comprising a support having coated thereon, on one surface, in order from the support, at least one icture recording photographic image or color-forming unit comprising at'leasf one silver halide emulsion layer and an auxiliary or sound track image recording radiation sensitive silver halide emulsion layer which does not form an image upon image-forming exposure of the picture recording units which comprises the following steps, including steps (B) and (C) in either sequence: (A) developing an auxiliary image record in the sound track areas comprising silver, (B) developing a picture record in the picture areas comprising silver and a nonditfusible dye, (C) contacting said auxiliary layer with a ballasted silver bleach inhibitor to adsorb said bleach inhibitor onto at least the silver of the auxiliary layer and (D) removing the bleachable silver images in the picture areas remaining after steps (B) and (C) and the residual or undeveloped silver halide.

Particularly useful photographic elements of the invention are those used for preparing multicolor motion picture film having a silver sound track and comprised of a film support having coated thereon, on one surface, in order (1) a plurality (generally three) picture recording photographic image or color-forming units, each unit comprising one or more (generally one or two) silver halide emulsion layers which are so disposed and sensitized that each unit is essentially sensitive to a different primary color region of the visible spectrum and (2) an auxiliary sound track image recording radiation sensitive silver halide emulsion layer which does not form an image upon image-forming exposure of the picture recording units. The auxiliary layer preferably contains a substantially colorless nondiffusible compound (e.g., a photographic coupler) which reacts with oxidized aromatic primary amine color developing agent and which decreases the rate of diffusion of a ballasted silver bleach inhibitor through the auxiliary layer.

The picture recording layers processed in accordance with the invention are used to form subtractive dye images of the pictures to be recorded. The silver halide emulsion layers can form colors complementary to the color to which they are sensitive. For example, the blue sensitive layer can form a yellow dye image, the red sensitive layer can form a cyan dye image and the green sensitive layer can form a magenta dye image. Alternatively, Th se layers can be falsely sensitized, i.e., they can form colors not complementary to the color to which they are sensitive. If so desired, the layers can be used to form a dye or a mixture of dyes which appear to have a neutral density.

The present system can be used either in the negativepositive system of photography or the reversal system of photography.

In order to form subtractive dyes, the photographic elements are processed in the presence of photographic color formers which can be incorporated in the silver halide emulsion layers or introduced into the system with the color developer. Photographic color formers are well known and are also referred to as photographic couplers or color couplers. In the well known three color system of subtractive color photography, S-pyrazolone couplers form magenta dyes, phenolic couplers including naphtholic couplers form cyan dyes and open-chain ketomethylene couplers form yellow dyes.

When processing photographic elements that do not contain incorporated couplers, the exposed element is processed in the presence of a coupler-developer composition which contains both a dilfusible photographic developing agent such as the aromatic primary amines and a difllrsible photographic color coupler. The oxidized photographic developing agent couples with the diifusible color coupler to produce a nondiffusible dye at the site of silver halide development. Suitable color couplers which can be used in coupler-developer compositions are shown in US. Patents 2,252,718; 2,592,243 and 2,950,970.

Preferably, the couplers are nondiffusible and are incorporated into the picture recording silver halide layers. The exposed element is then processed in the presence of an aromatic primary amine color developing agent such as the well known p-phenylenediamines. The oxidized color developing agent resulting from the reduction of the latent silver halide image couple-s with the incorporated coupler to form a non-diffusible image dye. Examples of nonditfusible photographic couplers which can be incorporated into the picture reo'ording silver halide emulsion layers of our novel photographic element are the pyrazolone couplers disclosed in US. Patents 2,343,702; 2,369,489; 2,436,130; 2,600,788; 2,006,759; 3,062,653; 3,311,476 and 3,419,391 and Belgian Patent 698,354, the phenolic couplers disclosed in US. Patents 2,367,531; 2,423,730; 2,474,293; 3,311,476; 3,419,390; 3,458,315 and 3,476,563 and the open-chain ketomethylene couplers disclosed in U.S. Patents 2,206,142; 2,436,130; 2,728,658 and 3,408,149. The layers can also contain other couplers such as the development inhibitor-releasing couplers disclosed in U .8. Patent 3,227,554 and the competing couplers disclosed in U.S. Patents 2,808,329; 2,689,793 and 2,742,832. Other useful incorporated coupler-s include the Fischer type couplers having both a ballast group and a solubilizing group which are rendered relatively insoluble and immobile in a hydrophilic colloid by a pH change during dispersion. Examples of such couplers are disclosed in U.S. Patents 1,108,028 and 2,186,849.

The auxiliary layer or sound track record layer of the photographic element of the invention is the light sensitive layer outermost from the support. For reasons that will become apparent, latent images of the picture record should not be formed in the auxiliary layer. The auxiliary layer is used in our novel elements only to record the sound track image. Exposure of the underlying picture recording layers can be made through the support, a filter layer between the auxiliary layer and the picture layers preventing exposure of the auxiliary layer during exposure of the picture layers. The auxiliary layer is then exposed separately from the emulsion side, the filter layer preventing exposure of the underlying picture layers. The filter layer is removed during subsequent processing. However, exposure of the underlying picture recording layers can be made through the auxiliary layer. Selective exposure of the auxiliary and picture recording layers can be attained by means of difierential photographic speed or spectral sensitivity of the silver halide of these layers. For example, the auxiliary silver halide emulsion layer can be sensitized to radiation to which the picture recording layers are at least partially insensitive such as infrared radiation. Sensitization to the region of relatively equal minimum sensitivity between two of the picture recording layers of adjacent spectral sensitivity is an alternative. Examples are those regions between the blue and green sensitive layers or the green and red sensitive layers of a color film having three color-forming units each primarily sensitive to a diflerent primary color region of the visible spectrum. In addition to or instead of being spectrally sensitized, the auxiliary layer can be of a different photographic speed. For example, the auxiliary layer can be spectrally unsensitized, i.e., it has only the native silver halide sensitivity to ultraviolet and near blue radiation. In this case, the auxiliary sound track recording layer should be sufiiciently slow so that it is not exposed upon exposure of the blue sensitive picture recording layer. Alternatively, the auxiliary layer can be sensitized to one of the primary color regions of the visible spectrum. Again, the auxiliary should be slower than the picture recording layer of corresponding spectral sensitivity. Photographic elements having certain of these spectral sensitivity and photographic speed relationships are the invention of Baptista and Smith and are disclosed in their eopending application entitled Novel Photographic Element, Ser. No. 100,614, filed Dec. 22, 1970.

The auxiliary superposed sound track recording layer acts in conjunction with the bleach inhibitor to prevent bleaching of the silver in the sound track area while permitting bleaching of developed silver in the picture area of the photographic element. This layer can be comprised simply of a silver halide emulsion. The silver halide content of this layer can vary widely such as from milligrams per square foot or less to 150 milligrams per square foot or more. The quantity of silver halide present in this auxiliary layer will have an effect upon the turbidity of the element and the sharpness of the image when viewed. For best results, it is therefore preferred that the auxiliary layer contain from about 10 milligrams per square foot to 100 milligrams per square foot silver halide, and preferably from about milligrams per square foot to about 75 milligrams per square foot. Particularly useful results are obtained when the auxiliary contains from about to 40 milligrams per square foot silver halide.

The grain size of the silver halide of the auxiliary layer can vary widely. For example, the average grain size can range from about 0.05 micron or less to about 0.5 micron or greater. Preferably, the grain size is as small as possible without requiring such high intensity exposure in the sound record area that the underlying picture recording layers in the sound area are over exposed causing a loss of definition of the sound record. An average grain size of from about 0.05 micron to about 0.2 micron is preferred.

The silver halide emulsions used in the auxiliary layer can be negative developing out emulsions or they can be fogged direct positive emulsions. They can comprise silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.

The auxiliary layer can also contain other addenda. For example, if the element is not to be processed in the presence of a coupler-developer composition, the picture recording layer or layers contain incorporated couplers and the auxiliary layer can contain one or more compounds which react with oxidized primary amine color developing agent. These compounds can be referred to as oxidized color developer scavengers. Their presence in the auxiliary layer is highly desirable as they serve to prevent the wandering of oxidized color developing agent from the points of silver halide development in the sound track area of the auxiliary layer into the picture area of the picture recording layers. If this Wandering should occur the oxidized color developing agent can couple with the incorporated couplers present in the picture area to yield dyes where none should have formed, thereby causing false coloration of the picture. The quantity of such a scavenger compound which is added to the auxiliary layer should be an amount at least sufiicient to consume that quantity of oxidized color developed agent which would be produced if all the silver halide in the auxiliary layer were developed to silver. The determination of the amount necessary can readily be made by one skilled in the art. Examples of such scavenger compounds include octylhydroquinone, dioctylhydroquinone, p-aminophenols, hydrazines, ascorbic acid derivatives and other compounds such as are disclosed in US. 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 as well as photographic color couplers. Certain nonditfusible color couplers such as those which can be incorporated into the picture recording silver halide layers increase the effectiveness of the auxiliary layer in preventing the diffusion of the bleach inhibitor into the picture recording layers in the picture area while allowing the diffusion of the bleach inhibitor into the sound track area. Couplers suitable for incorporation in the auxiliary layer of our novel system include those shown above as suitable for incorporation in the picture recording layers of the element.

The addition of these scavenger compounds and the color couplers in the silver halide emulsion layers used in the photographic films of the invention can be accomplished by a variety of known techniques. One of these techniques involves the use of certain organic solvents. These coupler solvents can be either of the low boiling or Water-sol ble type which are removed from the emulsion by evaporation or Washing following dispersion of the coupler and solvent in the emulsion or they can be of the high boiling, organic, crystalloidal type which remain incorporated in the emulsion. A description of the low boiling coupler solvents and the methods by which they can be used to disperse photographic couplers is found in Vittum et al., U.S. Patent 2,801,170, particularly at column 2, lines 3 to 32. Also, refer to US. Patent 2,861,170; Fierke et al., US. Patent 2,801,171, particularly at column 10, lines 33 to 51. High boiling, organic, crystalloidal coupler solvents are those which are substantially water-insoluble having a low molecular weight and a high boiling point (above about C. at atmospheric pressure). Examples of this type of coupler solvent include those shown in Fierke, US. Patent 2,801,171 at column 10, lines 22 to 32; Julian, US. Patent 2,949,360 at column 2, lines 3 to 18 and Jelley et al., US. Patent 2,322,027 at page 2, column '2, line 45 through page 3, column 2, line 6.

The selection of other addenda such as sensitizing dyes and the method of their incorporation in the silver halide emulsion of the auxiliary layer can be made by one skilled in the art who wishes to tailor the auxiliary emulsion for particular purposes and needs.

Gelatin or any conventional photographic hydrophilic colloid can be used as the vehicle for the silver halide in the auxiliary layer or in the silver halide emulsion layers comprising the picture recording units.

The ballasted silver bleach inhibitor used in the present system is adsorbed onto the silver of the sound record after initial development and before bleaching the silver by contacting the entire film with a solvent solution containing the bleach inhibitor. The solvent for the bleach inhibitor can be any solvent which will dissolve, alone or with other solvents, the bleach inhibitor and is compatible with hydrophilic colloid emulsions and the aqueous processing of these elements. Preferably, the solvent is predominately water but can be, for example, lower alkyl alcohols such as methanol, ethanol, isopropyl alcohol, butanol and the like.

The bleach inhibitor composition can be comprised of simply one or more bleach inhibitors in concentrations ranging from as little as 10- molar or less to 10- molar or more. Preferably, the concentration of bleach inhibitor ranges from about 10- to about 10* molar. The concentration of bleach inhibitor in the treatment compositions can vary depending upon the particular bleach inhibitor. For example, the concentration of bleach inhibitor can vary depending upon the hydrophilic nature of the bleach inhibitor. We have found that higher concentrations of the more hydrophilic bleach inhibitors often yield better results. On the other hand, less hydrophilic bleach inhibitors, e.g., those substituted with long alkyl chains yield satisfactory results at lower concentrations.

The bleach inhibitor composition, if predominately an aqueous solution, can contain, in addition to the bleach inhibitor, other compounds such as water-miscible organic solvents to aid in dissolving the other ingredients of the composition. The composition can also contain one or more compounds to produce a desired pH or to act as a buffering agent. The concentration of these compounds is determined by the quantity needed to achieve the desired result.

The pH of the aqueous ballasted bleach inhibitor composition can vary widely from mildly acidic of about pH 5 to strongly alkaline from about pH 12 or greater. Preferably, the pH of the solution is from about pH 6 to strongly alkaline and most preferably is from about pH 8 to about pH 12.5.

In addition to the above compounds, the aqueous bleach inhibitor composition can contain one or more water-soluble silver halide solvents or fixing agents such as ammonium, sodium or potassium sulfite, thiosulfate or thiocyanate or dithiooctandiol. The concentration of silver halide solvent can vary widely depending generally upon the particular bleach inhibitor used and the photographic element to which the composition is applied and can be determined by one skilled in the art according to guidelines set forth below. The silver halide solvents can be present in concentrations ranging from as little as 0.05% W. or less of the composition to W. or more of the composition. Preferably, the amount of silver halide solvent is from about 0.1% w. to about 2% w. of the solution.

The temperature at which the bleach lnhibitor can be brought into contact with the photographic element can vary Widely but preferably is approxlmately the same temperature as the remainder of the processing solutions. For example, photographic processing temperatures typically range from about 20 C. or less to 60 C. or higher. Temperatures of about 25 C., 40 C. and 50 C. are suitable in high speed processing procedures.

The time the bleach inhibitor is in contact with the silver sound record prior to being brought into contact with another processing solution can vary widely. It typically ranges from as little as 5 seconds or less to minutes or more. :Preferably, the film is contacted with bleach inhibitor for about 30 seconds to about 5 minutes.

The contact time for optimum results also can depend upon the hydrophilic nature of the bleach inhibitor and its rate of diffusion through the sound track emulsion layers. Hydrophilic bleach inhibitors can require a longer contact time to insure good coverage of the silver sound image. Slowly diffusing bleach inhibitors can also require a longer contact time to insure adequate penetration of the emulsion layers in the sound record area.

It was stated above that the bleach inhibitor treatment composition is brought into contact with the entire element, for example, by passing the element into a tank containing the bleach inhibitor composition and yet our method of processing the element comprises selectively adsorbing the bleach inhibitor onto only the silver of the sound track record subsequent to development and prior to bleaching. This is accomplished because of the auxiliary layer of the novel element. Due to the photographic speed or spectral sensitivity or both of the auxiliary layer, this layer will not have received exposure in the picture area and consequently will not contain any silver in the picture area subsequent to development. In the sound track area where exposure of the sound record was made with radiation of a wavelength and intensity suflicient to expose the auxiliary layer, it will contain developed silver according to this exposure. Depending upon the exposure, the underlying picture recording layers can also contain a silver sound record in the sound track area. The presence of this silver sound record in the underlying layers is not essential but is preferable since not all the silver for the proper sound track density must then be obtained from the auxiliary layer. This, therefore, allows a reduction in the silver halide content of the auxiliary layer resulting in a sharper, less turbid picture. When the bleach inhibitor composition is brought into contact with a photographic element having this auxiliary layer, this composition diffuses readily into the auxiliary layer. Those areas of the auxiliary layer which receive no exposure (the picture area) will contain only silver halide. Those areas of the auxiliary layer which receive exposure (the sound record area) will be comprised of silver and silver halide according to exposure. By controlling the length of time the bleach inhibitor composition is in contact with the element, the composition will not diffuse through the auxiliary layer into the underlying picture recording layers. Therefore, the only silver contacted by the bleach inhibitor composition is the silver present in the sound record area. The ballasted silver bleach inhibitor composition is such that the bleach inhibitor composition diifuses readily into and through the auxiliary layer Where silver is present (i.e., in the sound record area where the auxiliary layer was exposed). In those areas where no silver halide was reduced to silver (the picture area and the unexposed portions of the sound track area of the auxiliary layer) the rate of diffusion of the bleach inhibitor composition through the residual silver halide of the auxiliary layer is significantly less than the rate of diffusion of the bleach inhibitor composition through the developed silver. By controlling the length of time the photographic element is in contact with the bleach inhibitor, one can selectively bathe the silver in the sound record area, including part of the silver in the underlying layers, with bleach inhibitor composition While the silver in the underlying layers of the picture area is not significantly contacted. This result is obtained because the undeveloped silver halide in the auxiliary layer exhibits a barrier-like property to the bleach inhibitor. The silver in the underlying layers of the picture area not having been contacted with bleach inhibitor remains bleachable, is converted to a fixable silver salt and removed from the element when it is subsequently contacted with bleach and fix or bleach-fix solutions. The silver in the sound track area is protected by the bleach inhibitor against bleaching and this silver is not converted to a silver salt. Therefore, when the element is washed, the picture area will be substantially completely free of silver halide and metallic silver, while the sound track area will be comprised of metallic silver but will be free of residual silver halide. Hence, the silver halide in the auxiliary layer diminishes the rate of diffusion of the bleach inhibitor compound through the auxiliary layer and the bleach inhibitor does not pass through to the underlying picture recording layers where picture image silver can have developed. This silver thus remains unprotected from the subsequent bleaching operation.

As described hereinabove, the silver halide grain size of the auxiliary layer should be as small as in commensurate with the stated exposure requirement. It has been found that the smaller the grain size of the silver halide in the auxiliary layer, the more the residual silver hal de of the auxiliary layer diminishes the rate of diffusion of the bleach inhibitor through it. Since the rate of diffus on of the bleach inhibitor is less in a fine grained emulsion, the emulsion layer can be made thinner. This reduction of the auxiliary layer improves the sharpness of the picture record image as viewed through the auxiliary layer.

Also, as described hereinabove, the bleach inhibitor treatment composition can contain a silver halide solvent. The presence of such a compound increases the effectiveness of the auxiliary layer in preventing diffusion of the bleach inhibitor into the underlying picture recording layers of the picture area. As the silver halide solvent increases the barrier-like property of the residual silver halide of the auxiliary layer, it does allow a reduction in the silver halide content of this layer with the resulting improvement in sharpness and turbidity discussed above. For this reason, it is preferred the bleach inhibitor treatment composition contain a silver halide solvent. It is particularly preferred that the bleach inhibitor composition contain a silver halide solvent if the grain size of the auxiliary layer is relatively large since the use of the silver halide solvent increases the barrier etfectiveness of the layer. With an increase in barrier effectiveness, the quant1ty of silver halide in the auxiliary layer can be reduced thereby reducing turbidity and gaining in sharpness.

Since the silver halide solvent in the bleach inhibiting composition exhibits a fixing property, it is readily apparent that the amount of solvent present in the inhibitor composition should be at a minimum. If too much silver halide solvent is present, it will fix-out the silver halide from the auxiliary layer leaving the underlying silver images exposed to the bleach inhibitor. This silver would then become contacted with bleach inhibitor and not be subsequently bleached. Also, fixing-out too much silver halide would cause a build-up of silver halide in the inhibitor composition thereby reducing its effectiveness. Therefore, the amount of silver halide solvent in the bleach inhibitor composition should be that amount which increases the effectiveness of the auxiliary layer to a maximum and at the same time fixes out a minimum of silver halide. These bleach inhibitor compositions containing one or more silver halide solvents and an improved method of processing photographic elements to produce a silver auxiliary image or sound track are the invention of Baptista and are disclosed in his copending application entitled Novel Photographic Processing Compositions and Improved Processing Using Such Compositions for Preparing Silver Auxiliary and Sound Records, Ser. No. 100,776, filed Dec. 22, 1970, now abandoned and the continuation-in-part thereof filed concurrently herewith.

The elfectiveness of the auxiliary layer in preventing diffusion of the bleach inhibitor composition into the underlying picture recording layers is enhanced by use of color couplers or scavengers. This is particularly evident when the layer contains one or more -pyrazolone couplers. The effectiveness is enhanced even more if such an auxiliary layer is contacted with an alkaline bleach inhibitor composition preferably having a pH of or greater. It is believed that the couplers ionize under highly alkaline conditions and coact with the bleach inhibitor compound.

The effects of the coupler, silver halide solvent and high alkalinity of the bleach inhibitor composition each contribute to the effectiveness of the residual silver halide of the auxiliary layer as a barrier to the bleach inhibitor compound. The combined effects can be additive or even synergistic. If these various effects are taken advantage of, the effectiveness of the auxiliary layer can be increased sufficiently to allow a significant reduction in the silver halide content, thus decreasing the turbidity of the overcoated auxiliary sound track record layer and thereby increasing the sharpness of the picture record in the film.

The processing of exposed photographic elements having picture recording and auxiliary silver image or sound recording layers as described above is set forth below.

The processing of an exposed negative-positive system photographic element containing incorporated couplers is according to the following sequence:

(1) Color development (2) Stop bath (3) Bleach inhibitor (4) (A) Bleach-fix or (B) bleach and fix In the above procedure, steps (2) and (3) can be com; bined by a mixture of certain bleach inhibitors and a stop composition.

An exposed photographic element containing incorporated couplers can be reversal processed according to the following procedure:

(1) Black and white develop (2) Bleach inhibitor (3) Reversal expose in picture area only (4) Color develop (5) (A) Bleach-fix or (B) bleach and fix ('6) Wash An exposed photographic element not containing incorporated couplers can be reversal processed according to the following procedure:

12 (9) (A) Bleach-fix or (B) bleach and fix (10) Wash In the above two methods of reversal processing reversal fogging is accomplished with light which does not expose the auxiliary layer rather than by chemical fogging. This is done in order that dye images are not formed in the auxiliary layer in the picture area. Except for the different processing procedures required, the method to obtain a silver sound record or auxiliary image in a color photographic film by the method of our invention is the same for films prepared by both the negative-positive system and the reversal system.

As used herein and in the appended claims, the term ballasted bleach inhibitor refers to an organic compound which when in the form of a solution of the following composition:

Bleach inhibitor-l x 10- moles Water miscible solubilizer for bleach inhibitoras needed Water to make 1 liter pH adjusted to 12 which is brought into contact for 15 seconds up to 10 minutes at a temperature of 25 C. with a photographic element having two gelatino layers coated in a superposed relationship on one side of a support and having sound record and picture record areas in those layers, the underlying layer containing photographically developed silver in both areas and the outer layer containing in the sound track area silver photographically developed from silver halide of about 0.1 micron average grain size, coated at 140 mg. gelatin and 70 mg. silver per square foot, will prevent the bleaching of a sufficient amount of the silver in the sound record area to result in an infrared density of at least 1.20 measured at 900 nm. while not preventing substantially complete bleaching of the developed silver of the underlying layer in the picture when the element is treated for seconds at a temperature of 25 C. with a photographic bleach-fix solution of the following composition:

G. NaFeEDTA 1 (13% Fe) g 60 Na SO g NH SCN g 12 Na EDTA 1 g 7 Ammonium thiosulfate (60% solution) ml- 200 Water to 1 liter. pH 6.68.

1 EDTAEthylenedlamlne tetraacetic acid.

In conducting the above test, the contact time with the bleach inhibitor solution is selected to give highest sound record silver retention and lowest picture record silver retention, using the guidelines given above.

We have found that organic compounds which exhibit particular utility as ballasted bleach inhibitors as defined above are thioand selenol-containing compounds which are substituted with or contain a hydrophobic moiety such as a medium to long alkyl chain. One function of this moiety is to act as a ballast to control the rate of diffusion of the ballasted bleach inhibitor into the hydrophilic colloid of the silver halide emulsion layer. Examples of such compounds are mercaptoand selenol-substituted alkanoic acids, especially Z-mercapto alkanoic acids, thioland selenol-substituted aryls such as thiophenols, thionaphthols, alkyland alkylamidothiophenols and thionaphthols, ballasted thioland selenol-substituted heterocyclic compounds containing at least one nitrogen atom such as alkylamidomercaptobenzoxazoles, alkylamidomercaptobenzothiazoles, alkylamidomercaptobenzimidazoles, alkylamidomercaptothiadiazoles, alkylthiomercaptothiadiazoles, alkylamidomercaptotriazoles, l-alkylamidophenyl-S-mercaptotetrazoles and mercaptoquinolines, alkylamidoand alkylmercaptoquinolines, ballasted thiocarboxylic acids and esters thereof such as alkyland alkylamidothiobenzoic acid.

13 Particularly useful bleach inhibitors that can be used in the invention have the following general formulae:

a represents 0, l, 2, 3, 4, or 6;

X represents a member selected from the group consisting of sulfur and selenium;

R R R and R each represents a member selected from the group consisting of nitro; halo (e.g., chloro, bromo, fluoro, iodo); an alkyl group including substituted alkyl having from 1 to 22 carbon atoms and preferably having 5 to 18 carbon atoms, such as alkyl (e.g., methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl, secbutyl, tert-butyl, cyclobutyl, pentyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, cyclohexyl, cyclohexadienyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and the like), haloalkyl (e.g., fiuoroalkyl, chloroalkyl, bromoalkyl, as for example, chlorooctyl, bromododecyl, fiuorotetradecyl and the like), sulfoalkyl (e.g., sulfohexyl, sulfooctyl, sulfododecyl and the like), sulfatoalkyl (e.g., sulfatodecy, sulfatotetradecyl and the like), alkylsulfonylalkyl (e.g., ethylsulfonylbutyl and the like), cyanoalkyl (e.g., cyanohexy, cyanooctyl, cyanodecyl and the like), carboxyalkyl (e.g., carboxyhexyl, carboxyldecyl, carboxyhexadecyl and the like), aralkyl (e.g., benzyl, phendodecyl, tolyldodecyl and the like), alkoxyalkyl (e.g., octoxyhexyl, butoxyhexyl, ethoxydecyl and the like), aryloxyalkyl (e.g., phenoxymethyl, phenoxyethyl and the like), alkoxyaralkyl (e.g., methoxyphenylmethyl, butoxyphenylhexyl and the like), acyloxyalkyl (e.g., benzoyloxyhexyl, cetoxybutyl and the like), alkoxycarbonylalkyl (e.g., butoxycarbonylhexyl and the like), aryloxycarbonylalkyl( e.g., phenoxycarbonylethyl, chlorophenoxycar-bonylbutyl and the like), alkylamidoalkyl (e.g., hexanamidobutyl, octanamidopropyl and the like), arylamidoalkyl (e.g., phenylamidoethyl, methylphenylamidobutyl and the like) and the like; an aryl group including naphthyl and other fused ring aromatics and substituted aryl such as aryl (e.g., phenyl, naphthyl anthracenyl, phenanthrenyl and the like), haloaryl (e.g., chlorophenyl, trichlorophenyl, dibromophenyl, fluorophenyl, chlorotolyl and the like), sulfoaryl (e.g., sulfo' phenyl and the like), sulfatoaryl (e.g., sulfatophenyl and the like), nitroaryl (e.g., nitrophenyl, dinitrophenyl and the like), cyanoaryl (e.g., cyanophenyl, cyanonaphthyl and the like), carboxyaryl (e.g., carboxyphenyl, dicarboxyphenyl and the like), alkaryl (e.g., tolyl, butylphenyl, decylphenyl, diethylphenyl, trifluoromethylphenyl and the like), aralkaryl (e.g., benzylphenyl, naphthylmethylphenyl and the like), alkoxyaryl (e.g., octoxyphenyl, methoxyphenyl and the like), aryloxyaryl (e.g., phenoxyphenyl, phenoxynaphthyl and the like), acyloxyaryl (e.g., benzoyloxyphenyl, acetyloxyphenyl and the like), alkoxycarbonylaryl (e.g., ethoxycarbonylphenyl and the like), aryloxycarbonylaryl (e.g., phenoxycarbonylphenyl, methylphenoxycarbonylnaphthyl and the like), alkylamidoaryl (e.g., acetamidophenyl, amylamidophenyl, di-t-amylamidophenyl, hexanamidophenyl, heptanamidophenyl, octanamidophenyl, nonanamidophenyl, decanamidophenyl, undecanamidophenyl, dodecanamidophenyl, tridecanamidophenyl, tetradecanamidoaryl, pentadecanamidophenyl, heptafluorobutanamidophenyl, carboxycyclopentanacetamidophenyl and the like), cycloalkyliminosulfonylaryl( e.g., piperidinylsulfonylphenyl, azetidinylsulfonylphenyl, pyrrolidinylsulfonylphenyl indolinylsulfonylphenyl and the like) and the like; a thio group containing 3 to 22 carbon atoms such as alkylthio (e.g., propylthio, hexylthio, octylthio, dodecylthio and the like), carboxyalkylthio (e.g., carboxybutylthio, carboxylhexylthio, and the like), arylthio (e.g., phenylthio, naphthylthio, methylphenylthio and the like, alkylcarbonylalkylthio (e.g., methylcarbonylethylthio, butylcarboxylpropylthio and the like), alkylcarbonylarylthio (e.g., methylcarbonylphenylthio, hexylcarbonyltolylthio, benzylcarbonylphenylthio and the like), arylcarbonylarylthio (e.g. phenylcarbonylphenylthio and the like), arylcarbonylalkylthio (e.g., phenylcarbonylmethylthio and the like) and the like; an amido group containing from 4 to 22 carbon atoms such as alkylamido (e.g., hexanamido, heptanamido, octanamido, decanamido, heptafluorobutanamido and the like), arylamido (e.g., benzylamido and the like), alkarylamido (e.g., methylbenzylamido, butylbenzylamido, hexylbenzylamido, decylbenzylamido and the like), aralkylamido (e.g., phenacetamido, phenbutanamido, tolylhexanamido and the like), aryloxyalkylamido (e.g., phenoxyacetamido, naphthoxyacetamido, di-t-amylphenoxyacetamido and the like) and the like; a carbonyl group such as alkylcarbonyl (e.g., butylcarbonyl, heptylcarbonyl and the like), arylcarbonyl (e.g., phenylcarbonyl, naphthylcarbonyl and the like, alkoxycarbonyl (e.g., ethoxycarbonyl, butoxycarbonyl and the like), aryloxycarbonyl (e.g., phenoxycarbonyl, naphthoxycarbonyl and the like) and the like; a carbamoyl group such as alkylcarbamoyl (e.g. butylcarbamoyl, hexylcarbamoyl and the like), arylcarbamoyl (e.g., phenylcarbamoyl, naphthylcarbamoyl and the like) and the like; alkoxy (e.g., ethoxy, butoxy, octoxy, benzoxy and the like); aryloxy (e.g., phenoxy, toluoxy and the like);

R represents a member selected from the group consisting of hydrogen and an acyl group having from 1 to 22 carbon atoms including aryloyl and alkanoyl groups (e.g., benzoyl, acetyl, propanoyl, benzothioyl, acetothioyl and the like);

Y represents a basic cation such as an alkali metal ion like sodium and potassium, ammonium and the like;

A A A and A each represent a member selected from the group consisting of a carbonyl group C=O); a thiocarbonyl group C=S); a carboxymethylene group CH-COOH); a carbocyclic ring containing 3 to 6 carbon atoms which can be part of a fused ring structure such as cycloalkylene (e.g., cyclopropylene, cyclobutylene, cyclopentylene and cyclohexylene), cycloalkenylene (e.g., cyclopropenylene, cyclobutenylene, cyclopentenylene, cyclopentadienylene, cyclohexenylene and cyclohexadienylene) and arylene (e.g., phenylene, naphthylene, anthrylene and the like); a 3 to 6 membered heterocyclic ring containing at least one carbon atom and from 1 to 5 atoms selected from the group consisting of nitrogen, oxygen, sulfur and selenium which ring can have other carbocyclic and heterocyclic rings fused to it such as oxirenyl, furanyl, benzof-uranyl, isobenzofuranyl, dibenzofuranyl, oxazolyl, benzoxazolyl, isoxazolyl, benzisoxazolyl, oxadiazolyl, benzoxadiazolyl, 1,2-pyranyl, 1,4- pyranyl, 2'(H)benzopyranyl, 4(H)benzopyranyl, dioxolyl, methylenedioxybenzene, 1,2-oxazinyl, 1,3-oxazinyl, 1,4- oxazinyl, morpholinyl, 1,3-dioxolanyl, 1,-3-oxathianyl, 1,4- oxathianyl, 1,2-dioxanyl, 1,3-dioxanyl, 1,4-dioxany1, dioxanenyl, dioxadienyl, diazetyl, pyrrolyl, indolyl, isoindolyl, carb-azolyl, pyrrocolinyl, acridinyl, phenanthridinyl, Z-imidazolinyl, 3-imidazolinyl, 4-imidazolinyl, pyridyl, pyridazinyl, cinnolinyl, phthalazinyl, quinoxalinyl, pyrimidinyl, pyrazolo[3,4-d]pyrimidinyl, hypoxant-hinyl, 'benzopyrimidinyl, pyrazinyl, quinoxalinyl, phthalazinyl, quinolrnyl, isoquinolinyl, phenazinyl, phenoxazinyl, phen0thiazinyl, purinyl, pteridinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, triazolyl, benzotriazolyl, tetrazolyl, triazinthionyl, 1(H)azepinyl, piperidinyl, imidazolidinyl, quinolizidinyl, thienyl, 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-dithanyl, 1,4-dithiadienyl, selen-azolyl, benzoselenazolyl, isoselenazolyl, benzisoselenazolyl, selenadiazolyl, benzoselenadiazolyl and the like; such that R R, R and R do not represent a carbonyl group, a carbamoyl group or an amido group when A A A and A represent carbonyl or thiocarbonyl and such that the grouping R M-A the grouping R N-A the grouping R tA i and the grouping R QAQ each represent a moiety having a molecular weight of from 125 to 1,000 and preferably from 175 to 400 and preferably containing not more than one solubilizing group such as cal-boxy unless the grouping contains a hydrophobic moiety such as a long alkyl chain or an aryl group and such that when A A A and A represent a carbocyclic or a heterocyclic ring said ring has attached to it a hydrophobic moiety such as the atoms necessary to complete a 5 to 6 membered carbocyclic or heterocyclic ring fused to said ring; an alkyl group having from 6 to 18 carbon atoms; an alkylamido group having from 6 to 18 carbon atoms and an aryl group such as phenyl, naphthyl and an alkylamidoaryl group having 6 to 18 carbon atoms in the alkyl moiety and the like or has attached to it a plurality of such hydrophobic moieties, the total effect of which is to impart similar hydrophobic character such as two alkylamido groups having 3 to 12 carbon atoms and two alkylamidoaryl groups having 3 to 12 carbon atoms in the alkyl moiety.

Many heterocyclic compounds having a molecular weight of less than 100 (exclusive of the mercapto group) such as those compounds shown in British Patent 1,138,- 842 have been found not to be bleach inhibitors but rather bleach accelerators. Compounds of this type do not fall within the meaning of the term bleach inhibitor as defined herein.

In a more preferred embodiment of our invention, the bleach inhibitor is an organic compound or the salt of an organic compound as defined in Formulae I, II and III above having an acidic thiol or selenol, or having a group capable of forming such a compound prior to or subsequent to being brought into contact with a photographic element. For example, such thiol and selenol precursors can form the thiol or selenol group upon hydrolysis. Examples of precursors which form acidic thiol bleach inhibitors are bleach inhibitors LXIII and LXIV. Examples of compounds which can be treated to increase the number of acidic thiol groups are bleach inhibitors IX and X. Another example of thiol-forming compounds are disulfides (i.e., compounds of Formula II above) which cleave at the sulfur atoms to yield at least one thiol compound."

The acidity of the thiol and selenol groups can be imparted by the group to which these groups are attached (e.g., a heterocyclic or c'arbocyclic ring). Alternatively, other groups attached to the group having the thiol and selenol groups can impart acidity. For example, a carboxylic acid group on a carbon atom adjacent to the atom to which these groups are attached (e.g., 2-mercapto-lauric acid) imparts the desired acidity. Other electron withdrawing groups (e.g., nitro and halo) can also impart acidity to the thiol and selenol groups.

Compounds having the following formulae exhibit particular utility as bleach inhibitors in the present invention:

(IV) Z-mercaptobenzoxazoles (V) Z-mercaptobenzothiazoles (atria (VII) Z-mercaptothiadiazoles wherein:

R R R and R each represent an alkyl group having from 1 to 17 carbon atoms and preferably 5 to 12 carbon atoms;

R and R each represent an alkyl group having from 5 to 17 and preferably 8 to 12 carbon atoms;

Z represents sulfur or the group -NHCO-; and

n represents 1 to 5 and preferably 1.

The following list of compounds are typical sulfur and selenium compounds which function as bleach inhibitors in the present invention:

(I) Z-mercaptolauric acid (II) 4-octylthiobenzoic acid (III) 2-naphthalenethiol (IV) 4-butyl-2-naphthalenethiol (V) 2-quinolinethiol (VI) 4-quinolinethiol (VII) 4-hexy1-2-quino1inethiol (VIII) 5-pentyl-4-benzopyrimidinethiol (IX) 3-(S-mercapto-1,2,4-triazol-3-ylthio)-propanoic acid (X) I-(S-mercapto-1,2,4-triazo1-3-ylthio) -butan-2-one (XI) 3-mercapto-4-phenyl-5-n-undecyl-1,2,4-triazole (X11) 1- (3 -octa.namidophenyl -5-mercaptotetrazole (XIII) 1-(3-heptafiuorobutramido-phenyl)-S-mercaptotetrazole (XIV) 1-{3-[2-(2,4-di-t-amylphenoxy)-acetamido]- phenyl}-S-mercaptotetrazole (XV) 1- (4-rnethoxybenzyl -5-mercaptotetrazole (XVI) 1- [4-( l-piperidinylsulfonyl)-phenyl]-5-mercaptotetrazole (XVII) 1-(3-trifluoromethylphenyl)-5-mercaptotetrazole (XVIII) 1-( l-naphthyl -5-mereaptotetrazole (XIX) l-(2-naphthyl)-5-mercaptotetrazole (XX) 1-(3-pentanamidophenyl)-5-mercaptotetrazole (XXI) 1-(3-hexanamidophenyl)-5-mercaptotetrazole (XXII) 1-(3-heptanamidophenyl)-5-mercaptotetrazole (XXIII) 1- 3-octanamidophenyl -5-mercaptotetrazole (XXIV) 1-(3-nonanamidophenyl)-5-rnercaptotetrazole (XXV) 1-(3-decanamidophenyl)-5-mercaptotetrazole (XXVI) 1-(3-undecanamidophenyl)-5-mercaptotetrazole (XXVII) 1-(3-dodecanamidophenyl)-5-mercaptotetrazole (XXVIII) I-(Z-tridecanamidophenyl)-5-mercaptotetrazole (CL) 4-(3octanamidophenyl)-2-selenazolylthio1 (CLI) S-benzamido-Z-benzoselenazolylthiol (CLII) -decanamido-3-benzoisoselenazolylthiol (CLIII) 4-(3-hexanamidopheny1)-3-isoselenazolylthiol (CLIV) 4-decanamido-2,1,3-selenadiazol-6-ylthiol (CLV) 4-(3-hexanamidophenyl)-2,1,3-benzoselen adiazol- 7-ylthiol (CLVI) Z-naphthaleneselenol (CLVII) l-(2,4-di-n-butanamidophenyl)-tetrazol-5- ylselenol (CLVIII) 1-(2,4,6-tri-acetamidophenyl)-tetrazolyl-5 ylselenol (CLIX) 1-(3-hexanamidophenyl)-tetrazol-S-ylselenol (CLX) 1-(3-heptanamidophenyl)-tetrazol-5-ylselenol (CLXI) 1-(3-octanamidophenyl)-tetrazol-5-ylselenol (CLXII) 1-(3-nonanamidophenyl)-tetrazol-5-ylselenol (CLXIII) 1-(3-decanamidophenyl)tetrazol-5-ylselenol (CLXIV) 1-(3-undecanamidophenyl)-tetrazol-5- ylselenol (CLXV) 1-(3-dodecanamidophenyl)-tetrazol-S-ylselenol (CLXVI 4,7-di-tert-amylamido-1,3-benzoselenazol- 2-y1selenol (CLXV II) 4,5 ,7-tri-acetamido-1,3-benzoselenazol- 2-ylseleno1 (CLXVIII) 6-octanamido-l,3-benzoselenazol-2-ylselenol (CLXIX) 6-nonanamido-l,3-benzoselenazol-Z-ylselenol ,(OLXX) 6-decanamido-l,3-benzoselenazol-Z-ylselenol (CLXXI) G-undecanamido-1,3-benzoselenazol-2- ylselenol (CLXXII) 6-dodecanamido-l,3-benzoselenazol-2- ylselenol (CLXXIII) S-Octanamido-l,3,4-selenadiazol-Z-ylselenol (CLXXIV) S-decanamido-1,3,4-selenadiazol-2-ylselenol (CLXXV) 5-octanamido-1,3,4-thiadiazol-Z-ylselenol (CLXXVI) S-decanamido-1,3,4-thiadiazol-2-ylselenol .(CLXXVII) 2-octylthio-1,3,4-thiadiazol-Z-ylselenol ,(CLXXVIII) 2-nonylthio-1,3,4-thiadiazol-2-ylselenol (CLXXIX) 2-decylthio-l,3,4-thiadiazol-2-ylselenol (CLXXX) 2-heptylthio-l,3,4-selenadiazol-2-ylselenol (CLXXXI) 2-octylthio-1,3,4-selenadiazol-2-ylselenol CLXXXII) Z-decylthio-l,3,4-selenadiazol-Z-ylselenol (CLXXXIII) oxalic-bis-N-[3 (S-mercaptotetrazol-l-yl)- anilide] (CLXXXIV) suberic-bis-N- [3-(S-mercaptotetrazol-lyl) -anilide] (CLXXXV) terephthalic-bis-N-[S-(S-mercaptotetrazol- I-yl) -a nilide] (CLXXXV I) disulfide,bis-1-(3-nonanamidophenyl)- tetrazol-l-yl (CLXXXVII) disulfide,bis- 1- 3-hexanamidophenyl) tetrazol-l-yl (CLXXXVIII) disulfide,bis-6-octanamido-1,3-benzothiazol-2-yl (CLXXXIX) disulfide,bis-6-hexanamido-1,3-benzothiazol-Z-yl (CXC) disulfide,bis-S-hexanamido-l,3,4-thiadiazol- (CXCI) disulfide,bis-S-nonanamido-1,3,4-thiadiazol- (CXCII) disulfide,bis-2-heptylthio-1,3,4-thiadiazol- (CXCIII) disulfide,bis-2-octylthio-1,3,4-thiadiazol- (CXCIV) 1-(3-octanamidophenyl)-5-mercaptotetrazole,

sodium salt (CXCV) 1- 3-nonanamidophenyl) -5-mercaptotetrazole,

potassium salt (CXCVI) 2-octy1thio-5-mercapto-1,3,4-thiadiazol,

ammonium salt The bleach inhibitors used in the invention are known compounds and can be prepared by known methods. For example, the alkylamido substituted benzoxazoles, benzothiazoles and benzoselenazoles can be prepared by reacting the corre p nd g ommercia ly available amino sub- 20 stituted compounds with an acid chloride. The 1-(3-alkylamidophenyl)-5-mercaptotetrazoles are prepared by similar methods as shown in US. Pat. No. 3,376,310. Other bleach inhibitors can be prepared by methods available in well known organic chemistry reference works.

The method of our invention is useful to prevent the bleaching of sound records by both bleach compositions and bleach-fix compositions. Bleach compositions contain, for example, potassium dichromate or potassium ferricyanide as the oxidizing agent. Bleach-fix compositions are those which contain an oxidizing agent such as an iron salt of EDTA and a silver halide solvent. In a bleachfix composition, the silver is oxidized to a silver salt which is then removed from the film all in a single solution. Bleach compositions, however, only oxidize the silver to a silver salt. This silver salt and residual silver halide are subsequently removed by treatment with a separate fixing bath.

In general, bleaching compositions are more vigorous oxidizing compositions than bleach-fix compositions. For this reason, it is preferred that the silver of the sound record be protected by a less hydrophilic bleach inhibitor during bleaching of the picture record silver with a bleach composition. Examples of such compounds are those which are substituted with hydrophobic moieties such as a fatty chain.

The method of the invention is also applicable to the production of silver sound records in films in which the dye images are of a neutral density. Neutral density images can be formed from one or a mixture of couplers which react to form a neutral density dye or a combination of dyes which appear to be of neutral density. As with color image formation, subsequent to neutral density image formation the silver of the picture record is removed by bleaching and fixing. The silver sound record can be retained in this type of film by the use of the bleach inhibitors to yield a neutral density film having a picture record comprised of a dye or a mixture of dyes and a sound record comprised of silver. The terms picture record area and sound record area as used herein refer to areas of motion picture film as these areas can be seen in a plane view. Visualizing a strip of motion picture film and beginning with, for example, the left edge and proceeding to the right edge, the following areas are observed. Closest to the left edge are sprocket perforations used to transport the film via the means of sprockets through the apparatus associated with motion picture preparation and viewing. Adjacent to the sprocket perforations are the individual frames containing the picture record. These frames extend across a major part of the width of the film and the area between the side lines of the picture frames extending along the length of the film is referred to as the picture record area. To the right of and adjacent to the picture record area is the sound track or sound record area. This area is a narrow area extending along the length of the film. To the right of and adjacent to the sound record area is either the edge of the film or a second set of sprocket perforations which is adjacent to the right edge of the film.

A further understanding of our invention can be gained by reference to the drawing. The drawing depicts diagrammatically and sequentially the processing of one embodiment of our novel photographic element shown in cross-sectional view to produce a color picture record and a silver sound record. Processing is according to our novel method of processing. With reference to the embodiment shown in the drawing, transparent film support 22 has coated thereon gelatino-silver halide, blue sensitive, yellow-forming layer 23, gelatino-silver halide, red sensitive, cyan-forming layer 24, gelatino-silver halide, green sensitive, magenta-forming layer 25 and gelatinosilver halide, blue-green sensitive magenta-forming auxiliary layer 26. The sensitivity of layer 26 is such that the sensitivity peak falls at about 480 run. The photographic speed of layer 26 is such that it is about 0.4 Log E slower than the slower of the blue (23) and green (25) sensitive layers when exposed at 480 nm. For simplicity in illustrating the invention, conventional interiayers and the overcoat have been omitted from the drawing. In stage 1 the element is exposed through the negative original depicted for simplification of the figure as a single layer 21 coated on transparent support 20. Exposure for the picture record is made with white light and for the sound record with blue-green light having a bandspread of 470 to 490 nm. at half height. In practice, this original can be a multilayer element or a scene as viewed through a camera lens. Also, in practice, the picture record and the sound track record would generally be on separate originals and separate exposures made from each of these originals a short interval of time apart.

In carrying out the process of the invention as illustrated in the drawing subsequent to exposure, the latent image is developed in a color developer. The element then appears as in stage 2. Layers 23a, 24a and 25a in picture area 210 are comprised of silver and dye images. In picture area 29 these layers did not receive exposure and a latent image was not formed. Area 29 of these layers is thus comprised of silver halide. Auxiliary layer 26a, because of its photographic speed and spectral sensitivity, did not become exposed and is thus comprised of silver halide in both picture areas 29 and 210. Layers 23a, 25a and 26a, because of their photographic speed and spectral sensitivity, received sound track exposure and are comprised of silver and dye images in sound track area 27 and silver halide in sound track area 28. Layer 24a did not receive sound track exposure and is comprised of silver halide in both sound track areas 27 and 28. Subsequent to initial development and prior to bleaching, the element is contacted with a bleach inhibitor treatment composition. Stage 3 depicts the element subsequently to being contacted with the bleach inhibitor. The developed silver of picture area 210 in layers 23b, 24b and 25b is not contacted with bleach inhibitor because the silver halide of auxiliary layer 26b in picture area 210 acts as a barrier to the diffusion of the bleach inhibitor into the element. However, in sound track area 27 where auxiliary layer 26b contains developed silver, the bleach inhibitor difiuses into the element much more rapidly and becomes adsorbed not only to the sound record silver of layer 26b but also to the silver in the upper part of layer 25b. Thus, the silver in sound track area 27 of layers 26b and the upper part of 25b is protected against subsequent bleaching. By varying the time and other variables as discussed previously, the depth of diffusion of the bleach inhibitor into the element in sound track area 27 can be varied. Stage 4 depicts the element subsequent to bleaching and fixing or bleachfixing and washing of the element. Layers 23c, 24c and 250 in picture area 29 are clear, the residual silver halide having been fixed out. Picture area 210 of these layers is comprised of dyes, the developed silver having been bleached and fixed out. Auxiliary layer 26c in picture areas 29 and 210 is now clear, the residual silver halide having been fixed out. All four layers in sound track area 28 and layer 240 in area 27 are clear, the residual silver halide having been fixed out. Layer 23c and the lower part of layer 250 in sound track area 27 are comprised of dye, the developed silver in these layers having been bleached and fixed out since it was not contacted with bleach inhibitor prior to bleaching. Layer 26c and the upper part of layer 250 are comprised of silver and dye in sound track area 27 since these areas were contacted with bleach inhibitor. The processed element is thus comprised of a dye picture record and a silver sound record. It can thus be seen that the silver sound record of this processed element is obtained by simple processing techniques and without separate treatment of any part of the film.

Certain of the bleach inhibitors used in the present process can be substituted onto photographic color couplers in the coupling position through the thiol or selenol group. These couplers can then be incorporated into an auxiliary silver halide layer similar to that described herein coated on a novel photographic element which is exposed to a picture and sound record and chromo genically developed. The oxidized color developer resulting from development of the latent sound record in the auxiliary layer reacts with the incorporated bleach inhibitor substituted coupler to couple off a moiety which forms a bleach inhibitor. This imagewise released bleach inhibitor contacts the developed silver of the sound record in at least the auxiliary layer and renders it unbleachable. The auxiliary layer in the picture area is not exposed. Consequently, no development takes place in this area of the auxiliary layer and bleach inhibitor is not released. Therefore, all silver formed in the picture area remains bleachable. The processed element is comprised of a picture record comprised of dye and a sound record comprised of silver. Novel photographic elements containing these incorporated bleach inhibitor substituted couplers and the process for producing a motion picture film having a silver sound record from this element are the invention of Holtz and are described in the copending application entitled Film Containing Bleach Inhibitor Releasing Compounds and Process for Preparing Auxiliary Silver Image or Silver Sound Record Therewith, Ser. No. 100,610, filed Dec. 22, 1970, now abandoned, and the continuation-in-part thereof filed concurrently herewith.

Certain of the bleach inhibitors used in the present process can be incorporated into an auxiliary silver halide layer similar to that described above coated on a novel photographic element. The bleach inhibitors are incorporated as the free bleach inhibitor rather than substituted on a coupler as described above. The exposed element is chromogenically developed. The bleach inhibitor present in the auxiliary layer becomes adsorbed to the silver developed up in the sound record area. The picture area of the auxiliary layer not having been exposed contains only residual silver halide. Thus, only the silver of the sound record in the auxiliary layer is protected from bleaching. The processed element is comprised of a picture record comprised of dye and a sound record comprised of silver. The novel photographic element containing these incorporated bleach inhibitors and the process for producing a color film having a silver sound record from this element are disclosed and claimed in copending application Lestina, Kent and Holtz, entitled Film Containing Bleach Inhibitor and Process Therefor for Producing Color Film With Silver Sound Record, Ser. No. 100,613, filed Dec. 22, 1970 and the continuation-impart thereof filed concurrently herewith.

The following examples are included for a further understanding of the invention.

EXAMPLE 1 A multilayer color photographic motion picture negativepositive print film with a picture record area and a sound track record area and bearing on a transparent cellulose acetate film support three gelatino silver halide colorforming units sensitive to the blue, green and red regions of the visible spectrum and containing nondiffusible photographic couplers capable of forming nondiffusible yellow, magenta and cyan dye images, respectively, and outermost from the support an auxiliary gelatino silver chlorobromide mole percent chloride and 20 mole percent bromide) emulsion having an average grain size of about 0.1 micron coated at about 25 mg./ft. silver and 113 mg./ft. gelatin, and containing 45 mg./ft. magenta coupler 1-(6-chloro 2,4 dimethylphenyl) 3 [ix-(mpentadecylphenoxy)-butyramido]-5-pyrazolone (US. Pat. 3,062,653 at lines 10 to 20, column 4) is exposed for second through a Wratten 18-A filter (transmits radiation of 300 to 400 nm.) to a step tablet in the sound track area, and for ,6 second through a filter pack which results in a nearly neutral density exposure to a 21 step 0.15 Log E increment step tablet in the picture area and processed in the following baths:

Process temperature 38 C.

The chemical composition of the processing baths is as follows:

( 1) Prebath:

Borax (Na B O -l0H O) g 20 Sodium sulfate, desiccated g 100 Sodium hydroxide, 10% solution ml 10 Water to make 1 liter (pH 9.3). (3) Color developer:

Sodium hexametaphosphate g 2 Sodium sulfite, desiccated g 4 2 amino 5 diethylaminotoluenemonohydrochloride g 3 Sodium carbonate, monohydrate g 20 Potassium bromide g 2 Water to make 1 liter (pH 10.65). (5) Stop bath:

Acetic acid, glacial ml 24.5 Sodium bisulfite g 6.4 Water to make 1 liter (pH 3.76). (7) Bleach inhibitor bath:

Bath A:

Sodium carbonate, monohydrate g 6.2 Bleach inhibitor moles 1.155 10* Water to make 1 liter. pH adjusted to 10.0. Bath B:

Sodium carbonate g 6.2 Bleach inhibitor moles 1.155 X10" Sodium sulfite g 6.3 Water to make 1 liter. pH adjusted to 10.0. Bath C:

Identical'to Bath 7A except pH adjusted to 12.1 Bath D:

Identical to Bath 7B except pH adjusted to 12.1 (9) Bleach-fix:

Hydrochloric acid, conc. ml 9.2 Sodium sulfite g 12 Ammonium iron EDTA (1.56 molar solution) ml 92 Ammonium thiosulfate (60% solution) ml 200 Water to make 1 liter (pH 6.5).

(11) Stabilizer: Ml. Formaldehyde (37% w. solution) 20 Triton X-100, octylphenoxypolyethoxyethanol 0.6 Water to make 1 liter.

The bleach inhibitor bath is applied to the entire element. The silver density of the sound track record area after processing is measured at 900 mm. on a densitometer in the step of maximum density. The picture record area silver density is measured in a similar manner at the tenth step of the step exposure. Sufficient dye density is obtained at this step to be considered as D The results obtained from several bleach inhibitors are shown in Table I.

TABLE I Silver density Sound Picture Bleach lnhlbitor Bath (DmnL) (10th step) l-(3-nonalnamidophenyl)-5-mercapto- 7A 2. 92 0. 21

azo e. 1-(3-decanamldophenyl)-5-mercapto- 7A 2. 81 0. 10

tetrazole. 1-(3-undecanamidophenyl)-5-mercapto- 7A 2. 04 0. 05

tetrazole. 2-nonanamido-5-mercapto thiadiazole 7A 2. 00 0. 06 2-nonanamido-5-mercapto-l,3,4=-trlazole 7A 2. 28 0. 06 fi-nonanamido-Z-mercapto 1,3-benzo- 7A 2. 37 0. 07

thiaZole. 2-n1ercaptolauric acid 7A 1.90 0.06 5-nonauamido-2-mercapto-1,3-benzimid 7C 2. 26 0. 06

HZ 8. 1-(3-heptanamidophenyD-S-mercaptotet- 7B 2. 78 0. l4

raz e. 1-(3-pctanamidophenyl)-5-n1ercaptotetra- 7B 2. 52 0. 08

20 e. 6-heptanamido-2-mercapto-1,3-benzo- 7B 2. 72 0. 06

thiazole. l-(3-suberamidophenyl)-5-mercaptotet- 7B 2. 88 0. 06

raz 6. 2 quinolinylthiol 7B 1. 68 0. l1 Naphthalenethiol 7D 1. 45 0. 05

The above results demonstrate that a variety of compounds are etfective in preventing the bleaching of the sound record silver while allowing the silver of the picture record area to be bleached in our novel photographic element. When the same film is exposed to a multicolor image as well as a sound record and processed as above using the above compounds as bleach inhibitor, films are obtained having yellow, magenta and cyan picture records substantially free of silver and excellent silver sound records.

EXAMPLE 2 Multilayer color photographic motion picture negativepositive print films with picture and sound track record areas and bearing on a transparent support three gelatino silver halide color-forming units as in Example 1 and outermost from the support an auxiliary gelatino silver halide layer containing as follows:

Film: Contents A 25 mg./ft. silver as silver chlorobromide (/20) of about 0.2 micron average grain size and 113 mg./ft. gelatin.

B As in A plus the magenta coupler of Example l and tricresylphosphate as a coupler solvent.

C As in B except without coupler solvent.

are exposed through a 21 step 0.15 Log E increment step exposure object in the sound track area and through a Wratten 28, 025R, 0.20M and 0.10 neutral density filter pack to the same exposure object in the picture area and processed as follows:

(1) Prebath15 sec.

(2) Wash-15 sec.

(3) Color develop-8 min., 45 sec. (4) Wash-15 sec.

(5) Stop bath--2 min.

(6) Wash1 min.

(7) Bleach inhibitor bathl min. (8) Wash-1 min.

(9) Bleach-fix-Z min.

(10) Wash-6 min.

(11) Stabilizer-l5 sec.

Process temperature24 C.

The chemical composition of the processing baths is the same as in Example 1 except bleach inhibitor bath (step 7) which has the composition as specified below. The results shown in Table II demonstrate the advantage of incorporating a silver halide solvent in the bleach inhibitor bath. Picture and sound track record silver densities are measured in the same manner as in Example 1. The bleach inhibitor baths have the following chemical composition:

Series 1: G. Trisodium phosphate, dodecahydrate 19.0

1 (3 nonanamidophenyl) 5 mercaptotetrazole Sodium thiocyanate (as silver halide solvent if specified) 2.0 Water to make 1.0 liter. pH adjusted to 12.1. Series 2:

Trisodium phosphate, dodecahydrate 19.0 1 (3 nonanamidophenyl) 5 mercaptotetrazole 0.4 Sodium sulfite (as silver halide solvent if specified) 10.0 Water to make 1.0 liter. pH adjusted to 12.1.

TABLE II Silver density (Dam) Without silver With silver halide solvent; halide solvent Film Picture Sound Picture Sound 0. 88 1. 96 0. 04 2. 0.38 1.98 0. 0a 1.90 0. as 1. 9s 0. 1. 86 0.88 1.96 0.04 2.18 0. 38 1.98 0. 05 2.08 0.68 1. 95 0.14 1.96

The above results demonstrate the effectiveness of the auxiliary layer to prevent the diffusion of the bleach inhibitor into the underlying picture recording layers in the picture record area and thereby prevent the bleaching of silver in these layers is markedly increased by the incorporation of a silver halide solvent into the bleach inhibitor bath. Similar results are obtained when other silver solvents such as sodium thiosulfate and dithiooctanethial are substituted for the above silver solvents. The silver densities retained in the picture area in those series which did not use a silver halide solvent in the bleach inhibitor bath are greater than are possible to obtain without the use of such a solvent. The auxiliary layer of these films is comprised of silver halide of larger grain size than the auxiliary layer of the film of Example 1 wherein the bleach inhibitor bath did not contain a silver halide solvent. The above results demonstrate that it is preferable to use a bleach inhibitor bath containing silver halide solvent when the auxiliary layer is relatively thin and contains silver halide of larger grain size. When the above films are exposed to a multicolor image as well as a sound track record and processed as above using bleach inhibitor baths containing a silver halide solvent, motion picture films having yellow, magenta and cyan picture records substantially free of silver and an excellent sound record comprised of silver are obtained.

EXAMPLE 3 A multilayer color film similar to that of Example 1 is exposed as in that example and processed as follows:

(1) Prebath-15 sec.

(2) Wash15 sec.

(3) Color develop-8 min., 45 sec.

(4) Wash15 sec.

(5) Combined stop and bleach inhibitor bath-2 min. (6) Wash--1 min.

(7 Bleach-fix2 min.

(8) Wash6 min.

(9) Stabilizer-10 sec.

Process temperature24 C.

26 The chemical composition of processing baths 1, 3 and 9 is the same as baths 1, 3 and 11 of Example 1. The composition of the other baths is as shown below:

(5) Combined stop and bleach inhibitor bath: G. Trisodium phosphate, dodecahydrate 33.0 Sodium sulfite 9.45 1-(3-octanamidophenyl)-5-mercaptotetrazole 0.35 Water to make 1 liter. pH adjusted to 6.0.

(7) Bleach-fix bath:

Sodium ferric EDTA g 60.0 Sodium sulfite g 12.0 Ammonium thiosulfate (60% solution) ml 200 T etrasodium EDTA g 6.7

Water to make 1 liter (pH 6.8).

The sensitometric data obtained from the processing described above demonstrates that the results achieved are essentially identical to those obtained from processing the film according to a procedure similar to that of Example 2 above wherein the stop bath and bleach inhibitor bath are separate steps. When the above film is exposed to picture and sound records and processed as above, a dye picture record substantially free of silver and an excellent silver sound record are obtained as in Example 2.

EXAMPLE 4 A multilayer color photographic motion picture negative-positive print film similar to that of Example 1 is similarly exposed and processed as in Example 2. The composition of the processing baths is the same as in Example 2 except the bleach inhibitor bath (step 7) which has the composition specified below:

( 7) Bleach inhibitor:

Water to make 1 liter. pH adjusted to 12.1.

The silver densities in the picture and sound record areas are measured as in Example 1 and are set forth in Table IV:

TABLE IV Silver density Dmfll.)

Sound Picture record record The above results demonstrate that a silver sound record can be retained during bleaching of the silver of the picture record regardless of whether the bleach inhibitor bath is alkaline or acidic. When the above film is exposed to picture and sound record negatives and processed as above, the processed film has a dye picture record substantially free of silver and an excellent silver sound record regardless of whether the process used an alkaline or acidic bleach inhibitor bath.

27 EXAMPLE 5 Multilayer color photographic motion picture negativepositive print films bearing on a transparent support three gelatino silver halide color-forming units similar to those of Example 1 and outermost from the support a gelatino silver halide auxiliary layer as described in Example 1 and containing coupler solvent as indicated in Table V below and suflicient magenta coupler of Example 1 to react with the oxidized color developer which would result from developing all the silver halide present in the auxiliary layer are exposed and processed in a manner similar to that of Example 2 except that the bleach inhibitor bath is of the following composition:

(7) Bleach inhibitor bath: G. Trisodiumphosphate 19.0 Sodium sulfite 9.45

1-(3-nonanamidophenyl)-5-mercaptotetrazole 0.4 Water to make 1 liter.

pH adjusted to 12.1.

The silver densities are measured in a manner similar to that of Example 1 and are set forth in Table V.

TABLE V Auxiliary layer Silver density Silver halide} 2 Coupler Picture Sound mgJft. slvent record record 1 Expressed as the quantity of silver present.

3 The silver halide in the auxiliary layer of the films having a number sufiixed with A is of approximately the same grain size as the silver halide of the smallest grained color-forming unit. Those films having a number sutfixed with B have silver halide in the auxiliary layer of smaller grain size than the smallest grained color-forming unit.

a The coupler solvent is present in the ratio of one-half weight unit of coupler solvent per one weight unit of coupler.

The above results demonstrate satisfactory silver sound records can be retained during bleaching of the silver of the picture record when the auxiliary layer contains very low levels of silver halide. When films 4 A and 8B are processed under modified conditions satisfactorily low silver densities in the picture record are obtained while sufiiciently high silver densities are retained in the sound record. When the above films are exposed to a multicolor picture negative and a sound record negative and processed as above, motion picture films having yellow, magenta and cyan dye picture records substantially free of silver and excellent silver sound records are obtained.

EXAMPLE 6 A single layer photographic motion picture negativepositive print film with picture and sound record areas and bearing on a transparent support a blue sensitive gelatino silver halide layer similar to the auxiliary layer of Example 1 and containing oxidized color developer acceptor and coupler solvent as indicated below is given the same exposure in both the picture and sound recording areas to a 21 step 0.15 Log E increment step exposure object and processed as follows:

(1) Color develop-8 min., 45 sec. (2) Wash sec.

(3) Stop-fix2 min.

Process temperature24 C.

The chemical composition of the color developer is the same as in Example 1. The stop-fix bath is shown as fix bath SC in Example 7B. The silver densities are measured as in Example 1 and are shown below in Table VI-A.

TABLE VI-A Oxidized color Silver developer Coupler density, acceptor solvent h max.

None 0. 44 1 0. 56 1 0. 56 2 0. 57 3 0. 59 4 0. 57 None A- 0. 46 5 0. 56

e The oxidized color developer acceptors are present in the silver halide layer in a quantity sufficient to accept all the pXldlZBd color de veloper which would be produced if the silver hahde is completely exposed and developed. These acceptors are as follows:

1. The magenta coupler of Example 1. 2. 1-hydroxy-2-[A-(2,4-di-tert-amylphenoxy)-n-butyl]-naphthamide,

Coupler No. 1, U.S. Pat. 2,474,293. 3. a-Pivalyl-a-( i-carboxyphenoxy)-2-chloro-5-[v-(2,4-di-tert-amylpNherglxy)-butyramido]-acetanilide, U.S. Pat. 3,408,194, Coupler 4. Dioctylhydi-oquinone.

5. 1-phenyl-4-ethyl-3-[a-(3-m-pentadecylphenoxy)-butyramido]-5- pyrazolone, a coupler according to U.S. Pat. 2,998,314.

The coupler solvents are as follows:

A. Tricresyl phosphate: This solvent is present in the a mouut of one weight unit of solvent per two weight units of oxidized color developer acceptor.

B. Di-n-butyl phthalate: This solvent is present in the amount of one weight unit of solvent per weight unit of oxidized color developer acceptor.

The above results demonstrate that the presence of oxidized color developer acceptor results in significantly increased silver densities in the simulated auxiliary layer. In a mutilayer element containing incorporated couplers in the picture recording layers, the incorporation of oxidized color developer acceptor into the auxiliary layer offers the additional advantage of preventing false color formation by the wandering of oxidized color developer from the auxiliary layer in the picture area of the picture recording layers. A multilayer color motion picture negative-positive print film having picture and sound recording areas bearing on a transparent support three gelatino silver halide color-forming units similar to those of EX- ample 1, and outermost from the support an auxiliary gelatino silver halide layer as in Example 1 which contains sufiicient photographic magenta coupler (as specified below) to react with all the oxidized color developer Which would result from developing all the silver halide in the layer and tricresyl phosphate as coupler solvent present in the ratio of one weight of coupler solvent per two weights of coupler is exposed, processed and the silver densities measured in a manner similar to that of Example 1. The results are shown in Table VI-B.

TABLE VI-B Silver Density Sound Picture (D max.)

e The magenta couplers are as follows:

1. Coupler No. 1 in Table VII-A.

2. Coupler No. 5 in Table VII-A.

3. 1-(2,4,6-trichlorophcnyl)-3-{ 5-[a-(3-tert-butyl-4-liydroxyphenoxy)- tetradecanamidol-2-chloroanilinoi-5-pyrazolone, Coupler No. 11 of British Pat. 1,183,515.

4. 1-(2,4,6-trichlorophenyl)-3-l3-[a-(2,4-di-tert-amylphenoxy-acetamlgig-benzamidolopyrazolone, Coupler No. 7 of U.S. Pat. 2,600,-

The above results demonstrate that comparable amounts of silver are retained in the sound record areas of multilayer films having various different color couplers incorporated in the auxiliary layer. When the above films are exposed to a multicolor picture negative and a sound record negative and processed as above, yellow, magenta and cyan dye picture images substantially free of silver and excellent sound record images are obtained.

EXAMPLE 7 A multilayer color motion picture negative-positive print film having picture and sound record areas and bearing on a transparent support three gelatino silver halide emulsion color-forming units similar to those of Example 1 and outermost from the support an auxiliary gelatino silver halide emulsion layer containing 25 mg./ft. silver as silver chlorobromide (80/20), 113 mg./ft. gelatin, 45 mg./ft. magenta of Example 1 and 23 mg./ft. tricresyl phosphate as coupler solvent is exposed in the picture area to a multicolor test object and in the sound record area to a sound negative master and is processed as below:

(A) Bleach-fix procedure (1) Prebath sec 15 (2) Wash sec 15 (3) Color develop min 9 (4) Stop bath min 2 (5) Wash min 1 (6) Bleach inhibitor bath min 1 (7) Wash 90 30 (8) Bleach-fix min 3 (9) Wash min 5 (l) Stabilizer sec 30 Process temperature C..- 20

The chemical composition of processing baths 1, 3, 4 and 10 is the same as baths 1, 3, and 11 of Example 1. The composition of the other baths is as follows:

(6) Bleach inhibitor bath: G. Sodium carbonate 5.3 l-(B-decanamidophenyl)-5-mercaptotetrazole 4.0 Water to make 1.0 liter.

(8) Bleach-fix bath:

Hydrochloric acid, conc. rnl 9.2 Sodium sulfite g 12 Ammonium ferric EDTA (1.56 molar solution) ml 92 Ammonium thiosulfate (60% solution) ml 200 Water to make 1 liter.

The processed element is evaluated by measuring the maximum silver density at 900 mm. in the sound record area. The resu are shown in line A of Table VII below.

(B) Dichromate bleach procedure When the above procedure is repeated except that the element is treated with bleach inhibitor bath for 3 minutes and a dichromate bleach (4 min.), wash (1 min.) and fix (2 min.) are substituted for step 8 bleach-fix, the results shown in line B of Table VII are obtained. The composition of the substitute baths is as follows:

Water to make 1 liter.

(C) Ferricyanide bleach I When the procedure of part B above is repeated except that the element is treated with a ferricyanide bleach of the composition shown below for one minute, the results shown in line C of Table VIII are obtained.

(8C) Ferricyanide bleach I:

Water ml 800 Potassium ferricyanide g 35 Potassium bromide g 15 Sodium acetate g.. 20

Acetic acid to adjust pH to 5.0. Water to make 1 liter.

(D) Ferricyanide bleach H When the procedure of part B above is repeated except that the element is treated with a ferricyanide bleach of the composition shown below for 2 minutes, the results shown in line D of Table VII are obtained.

(8A) Ferricyanide bleach H: G. Potassium ferricyanide 35 Potassium bromide 15 Water to make 1 liter.

(E) Ferricyanide bleach II, modified bleach inhibitor bath When the procedure of part D above is repeated except that the element is treated with a bleach inhibitor bath of the composition shown below, the results shown in line B of Table VII are obtained.

(6) Modfied bleach inhibitor bath: G. Trisodium phosphate 8.2 1-(3-decanamidophenyl)-5-mercaptotetrazole 0.4 Water to make 1 liter.

TABLE VII Silver density (D max.)

Bleach Bound Picture Line A Bleach-fix 1. 18 0. 07 B Dichromate 1. 40 0. 10 C". Ferrlcyanlde I- 1. 42 0.10 D Ferrlcyanide II- 1. 12 0.10 E 1. 84 0. 10

EXAMPLE 8 A multilayer color motion picture reversal print film having picture and sound record areas and bearing in order on a transparent support gelatino silver halide red sensitive, cyan-forming unit, a gelatino silver halide green sensitive, magenta-forming unit, a yellow filter layer, a gelatino silver halide blue sensitive, yellow-forming unit and an auxiliary gelatino silver halide layer similar to the 31 auxiliary layer of Example 1 and containing an oxidized color developer acceptor is exposed to a multicolor picture record positive and a sound record negative and processed as follows:

Tempera- Bath Time ture, C.

1. Prehardener 2 minutes, 30 seconds. 35 2. Neutralizer- 30 seconds 35 3. First developer 2 minutes, seconds. 38 4. First stop 30 seconds 36 6. Wash- 30 seconds 38 6. Bleach inhibitor 1 minute 38 7. Wash 30 seconds 38 8. Reversal expose by light ..do 38 9. Color develop 2 minutes, 30 seconds. 43 10. Second stop 30 seconds 35 11. Wash- ...do. 38 12. Bleach 1 minute, 30 seconds 35 13. Fix. 0..-- 35 14. Wash 1 minute 38 16. Srnhilive 30 semnd 36 The chemical composition of the above processing baths is as follows:

( 1) Prehardener:

Water ml 800.0 p-Toluenesulfinic acid (sodium salt) g 1.0 Succinaldehyde, bis, bisulfite g 8.5 Magnesium sulfate, heptahydrate g 257.0 Sodium sulfate g 75.0 Sodium bromide g 2.0 Sodium acetate g 15.0 Formalin (37% by volume aqueous formaldehyde solution) --ml-.. 27.0 Glacial acetic acid --ml..- 2.4 N methylbenzothiazolium p toluene sulfonate g .03 Water to 1.0 liter.

(2) Neutralizer:

Water ml.. 800.0 Hydroxylamine sulfate g 18.0 Sodium bromide g 17.0 Glacial acetic acid ml 10.0 Sodium hydroxide g 6.8 Sodium sulfate g 50.0 Water to 1.0 liter. (3) First developer:

Water ml 800.0 Sodium tetraphosphate g 2.0 Sodium bisulfite g 8.0 1-pheny1-3-pyrazolidone g .35 Sodium sulfite g 37.0 Hydroquinone g 5.5 Sodium carbonate (anhydrous) g 28.2 Sodium thiocyanate g 1.38

Potassium iodide (1.0% by weight aqueous (9) Color developer:

Water ml 800.0 'Nitrilo (trimethylene phosphonic acid) sodium salt ml 3.0 Benzyl alcohol g 4.5 Sodium sulfite g 7.5 Trisodium phosphate- 12H O g 36.0 Sodium bromide g 0.9 Potassium iodide (0.1% w. solution) ml Sodium hydroxide g 3.25 Citrazinic acid g 1.5 4 amino-3-methyl-N-ethyl-N-(beta-methanesulfonamidoethyl) aniline sesquisulfate monohydrate g l 1.0 Ethylenediamine g 3.0 Water to make 1.0 liter.

(l2) Ferricyanide bleach: G. Borax (Na B O -SH O) 1.0 Sodium bromide 43.0 Sodium ferrocyanide (decahydrate) 245.0 Potassium persulfate 67.0 Carbowax 1540, sold by Union Carbide Chemical Co., a polyethylene glycol 3.6 Water to 1.0 liter.

(13) Fixing bath:

Water ml 800.0 EDTA (disodium salt) g 0.5 Sodium thiosulfate (pentahydrate) g 204.0 Sodium sulfite g 10.0 Disodium phosphate g 15.0 Water to 1.0 liter.

(15) Stabilizing bath: Ml.

Renex 30 (sold by Atlas Chemical Co., a polyoxyethylene ether alcohol) 0.14 Formalin (37% w. solution) 6.0

Water to 1.0 liter.

The processed film contains yellow, magenta and cyan dye picture images substantially free of silver and an excellent silver sound record.

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

We claim: I

1. The process of producing a picture record and an I auxiliary silver image record in an imagewise exposed photographic element comprising a support having coated thereon, on one surface in order, (1) a picture recording photographic image-forming unit comprising at least one silver halide emulsion layer and (2) an auxiliary image recording radiation sensitive silver halide emulsion layer which does not form an image upon image-forming exposure of said picture recording unit which comprises the following steps, including steps (B) and (C) in either sequence: (A) developing an auxiliary image record comprising silver, (B) developing a picture record in the picture areas comprising silver and a nondiffusible dye, (C) contacting said auxiliary layer with a ballasted silver bleach inhibitor to adsorb said bleach inhibitor onto at least the silver of the auxiliary layer and (D) removing the bleachable silver images in the picture areas remaining after steps (B) and (C) and the residual silver halide.

2. The process of claim 1 wherein said ballasted silver bleach inhibitor has an acidic thiol or selenol group.

3. The process of claim 1 wherein said ballasted silver bleach inhibitor has a formula selected from the group consisting of:

a represents 0, 1, 2, 3, 4, 5 or 6;

X represents a member selected from the group consisting of sulfur and selenium;

R R R and R each represent a member selected from the group consisting of nitro, halo, an alkyl group, an aryl group, a thio group containing from 3 to 22 carbon atoms, an amido group containing from 4 to 22 carbon atoms, a carbonyl group, a carbamoyl group, an alkoxy group and an aryloxy p;

R represents a member selected from the group consisting of hydrogen and an acyl group;

Y represents a basic cation;

A A A and A each represent a member selected from the group consisting of a carbonyl group, a thiocarbonyl group, a carboxymethylene group, a 3 to 6 membered carbocyclic ring and a 3 to 6 membered heterocyclic ring containing at least one carbon atom and at least one heteroatom selected from the group consisting of nitrogen, oxygen, sulfur and selenium such that -R R R and R do not represent a carbonyl group, a carbamoyl group or an amido group when A A A and A represent a carbonyl group or a thiocarbonyl group and such that the grouping R (A the grouping R -{-A the grouping R,, --(A and the grouping R,, (A each represent a moiety having a molecular weight of from 125 to 1,000 and such that when A A A and A represent a carbocyclic or a heterocyclic ring, said ring has attached to it at least one hydrophobic moiety.

4. The improvement of claim 3 wherein A A A and A represent a member selected from the group consisting of a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus, a thiadiazole nucleus, a triazole nucleus and a l-phenyltetrazole nucleus.

5. The process of claim 1 wherein said ballasted silver bleach inhibitor is a mercapto-substituted heterocyclic compound containing from 5 to 6 atoms in the ring, said ring containing at least one nitrogen atom.

6. The process of claim 5 wherein said ballasted silver bleach inhibitor is selected from the group consisting of an alkylamidomercaptobenzoxazole, an alkylamidomercaptobenzothiazole, an alkylamidomercaptobenzimidazole, an alkylamidomercaptothiadiazole, an alkylthiomercaptothiadiazole, an alkylamidomercaptotriazole and a 1-alkylamidophenyl-S-mercaptotetrazole.

7. The process of producing a picture record and a silver sound track record in a photographic element having imagewise exposed picture areas and imagewise exposed sound track areas comprising a support having coated thereon, on one surface in order, (1) a picture recording photographic image-forming unit comprising at least one silver halide emulsion layer and (2) an auxiliary sound recording radiation sensitive silver halide emulsion layer which does not form an image upon image-forming exposure of said picture recording unit which comprises the following steps, including steps (B) and (C) in either sequence: (A) developing a sound track record in the sound track areas comprising silver, (B) developing a picture record in the picture areas comprising silver and a nondiffusible dye, (C) contacting said auxiliary layer with a ballasted silver bleach inhibitor to adsorb said bleach inhibitor onto at least the silver of the auxiliary layer and (D) removing the bleachable silver images in the picture area remaining after steps (B) and (C) and the residual silver halide.

' 8. The process of claim 7 wherein said ballasted silver bleach inhibitor has an acidic thio or selenol group.

9. The process of producing a picture record and a silver sound track record in a photographic element having imagewise exposed picture areas and imagewise exposed sound track areas comprising a transparent support having coated thereon, on one surface in order, (1) a picture recording photographic color-forming unit comprising at least one silver halide emulsion layer which contains at least one photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nondifiusible dye and (2) an auxiliary sound recording radiation sensitive silver halide emulsion layer which does not form an image upon image-forming exposure of said picture recording unit, said auxiliary layer containing a colorless nondiifusible compound which reacts with oxidized aromatic primary amine color developing agent which comprises the following steps, including steps (B) and (C) in either sequence: (A) developing a sound track record in the sound track areas comprising silver, (B) developing a picture record in the picture areas comprising silver and a nondiffusible dye, (C) contacting said auxiliary layer with a ballasted silver bleach inhibitor to adsorb said bleach inhibitor onto at least the silver of the auxiliary layer and (D) removing the bleachable silver images in the picture areas remaining after steps (B) and (C) and the residual silver halide.

10. The process of claim 9 wherein said compound in said auxiliary layer is a photographic coupler.

11. The process of claim 10 wherein said ballasted silver bleach inhibitor has an acidic thiol or selenol group.

12. The process of claim 11 wherein said ballasted silver bleach inhibitor is a mercapto-substituted heterocyclic compound containing 5 to 6 atoms in the ring, said ring containing at least one nitrogen atom.

13. The process of claim 12 wherein said ballasted silver bleach inhibitor is selected from the group consisting of alkylamidomercaptobenzoxazole, an alkylamidomercaptobenzothiazole, an alkylamidomercaptobenzimidazole, an alkylamidomercaptothiadiazole, an alkylthiomercaptothiadiazole, an alkylamidomercaptotriazole and a 1-alkylamidophenyl-S-mercaptotetrazole.

14. The process of producing a photographic picture record and a silver sound track record in a photographic element having imagewise exposed picture areas and imagewise exposed sound track areas comprising a transparent support having coated thereon, on one surface in order, (1) three picture recording photographic imageforming units, each unit comprising at least one silver halide emulsion layer, which are so disposed and sensitized that each said unit is essentially sensitive to a diiferent primary color region of the visible spectrum and (2) an auxiliary sound recording radiation sensitive silver halide emulsion layer which does not form an image upon imageforming exposure of said picture recording units which comprises the following steps, including steps (B) and (C) in either sequence: (A) developing a sound track record in the sound track areas comprising silver, (B) developing a picture record in the picture areas comprising silver and a nondilfusible dye, (C) contacting said auxiliary layer with a ballasted silver bleach inhibitor to adsorb said bleach inhibitor onto at least the silver of the auxiliary layer and (D) removing the bleachable silver images in the picture areas remaining after steps (B) and (C) and the residual silver halide.

15. The process of claim 14 wherein said auxiliary layer contains a compound which reacts with oxidized aromatic primary amine color developing agent.

16. The process of claim 15 wherein said compound in said auxiliary layer is a photographic color coupler.

17. The process of claim 16 wherein said ballasted silver bleach inhibitor has an acidic thiol or selenol group.

18. The process of claim 16 wherein said ballasted silver bleach inhibitor has a formula selected from the group consisting of:

(I) R (A )XR (II) RJGAQX-XQiR; I II) R (-A }X Y wherein:

a represents 0, 1, 2, 3, 4, 5 or 6; X represents a member selected from the group consisting of sulfur and selenium;

R R R and R each represent a member selected from the group consisting of nitro, halo, an alkyl group, an aryl group, a thio group containing from 3 to 22 carbon atoms, an amido group containing from 4 to 22 carbon atoms, a carbonyl group, a carbamoyl group, an alkoxy group and an aryloxy p;

R represents a member selected from the group consisting of hydrogen and an acyl group;

Y represents a basic cation;

A A A and A each represent a member selected from the group consisting of a carbonyl group, a thiocarbonyl group, a carboxylmethylene group, a 3 to 6 membered carbocyclic ring and a 3 to 6 membered heterocyclic ring containing at least one carbon atom and at least one heteroatom selected from the group consisting of nitrogen, oxygen, sulfur and selenium such that R R R and R do not represent a carbonyl group, a carbamoyl group or an amido group when A A A and A represent a carbonyl group or a thiocarbonyl group and such that the grouping R tA the grouping R {-A the grouping R (-A and the grouping Rf-GAQ each represent a moiety having a molecular weight of from 125 to 1,000 and such that when A A A and A represent a carbocyclic or a heterocyclic ring, said ring has attached to it at least one hydrophobic moiety.

19. The process of claim 18 wherein A A A and A represents a member selected from the group consisting of a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus, a thiadiazole nucleus, a triazole nucleus and a l-phenyltetrazole nucleus.

20. The process of claim 16 wherein said ballasted silver bleach inhibitor is a mercapto-substituted heterocyclic compound containing 5 to 6 atoms in the ring, said ring containing at least one nitrogen atom.

21. The process of claim 20 wherein said ballasted silver bleach inhibitor is selected from the group consisting of an alkylamidomercaptobenzoxazole, an alkylamidomercaptobenzothiazole, an alkylamidomercaptobenzimidazole, an alkylamidomercaptothiadiazole, an alkylthiomercaptothiadiazole, an alkylamidomercaptotriazole and 1-alkylamidophenyl-S-mercaptotetrazole.

22. The process of producing a picture record and a silver sound track record in a photographic element having imagewise exposed picture areas and imagewise exposed sound track areas comprising a transparent support having coated thereon, on one surface in order, (1) three picture recording photographic color-forming units, each unit comprising at least one silver halide emulsion layer, which are so disposed and sensitized that each unit is essentially sensitive to a different primary color region of the visible spectrum and contains a nondiffusible photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nondifiusible dye essentially complementary in color to one of the primary color regions of the visible spectrum and (2) an auxiliary sound recording silver halide emulsion layer which does not form an image upon image-forming exposure of said picture recording units, said auxiliary layer containing a colorless nonditfusible compound which reacts with oxidized aromatic primary amine color developing agent which comprises the following steps, including steps (B) and (C) in either sequence: (A) developing a sound track record in the sound track areas comprising silver, (B) developing a picture record in the picture areas comprising silver and a nonditfusible dye, (C) contacting said auxiliary layer with a ballasted silver bleach inhibitor to adsorb said bleach inhibitor onto at least the silver of the auxiliary layer and (D) removing the bleachable silver images remaining in the picture areas after steps (B) and (C) and the residual silver halide.

23. The process of claim 22 wherein said compound in said auxiliary layer is a photographic color coupler.

36 24. The process of claim 23 wherein said photograpnh color coupler in each of said picture recording layers forms a dye essentially complementary in color to the sensitivity of the emulsion in which it is incorporated.

25. The process of claim 24 wherein said ballasted silver bleach inhibitor has the following formula:

wherein n represents a positive integer from 1 to 5 and R represents an alkyl group having from 1 to 17 carbon atoms.

26. The process of claim 25 wherein n represents 1 and R represents an alkyl group having from 5 to 12 carbon atoms.

27. The process of claim 24 wherein said ballasted silver bleach inhibitor has the following formula:

wherein n represents a positive integer of from 1 to 5 and R represents an alkyl group having from 1 to 17 carbon atoms.

28. The process of claim 27 wherein n represents 1 and R represents an alkyl group having from 5 to 12 carbon atoms.

29. The process of claim 24 wherein said ballasted silver bleach inhibitor has the following formula:

( rgit wherein n represents a positive integer of from 1 to 5 and R represents an alkyl group having from 1 to 17 carbon atoms.

30. The process of claim 29 wherein n represents 1 and R represents an alkyl group having from 15 to 12 carbon atoms.

31. The process of claim 24 wherein said ballasted silver bleach inhibitor has the following formula:

Eat theta wherein R represents an alkyl group having from 5 to 17 carbon atoms.

34. The process of claim 33 wherein R represents an alkyl group having from 8 to 12 carbon atoms.

37 35. The process of claim 24 wherein said ballasted silver bleach inhibitor has the following formula:

wherein n represents a positive integer of from 1 to and R represents an alkyl group having from 1 to 17 carbon atoms.

36. The process of claim 35 wherein n represents 1 and R represents an alkyl group having from 5 to 12 carbon atoms.

37. The process of producing a picture record and a silver sound track record in a photographic element having imagewise exposed picture areas and imagewise exposed sound track areas comprising a transparent support having coated thereon, on one surface in order, (1) three picture recording photographic color-forming units, each unit comprising at least one silver halide emulsion layer, which are so disposed and sensitized that each said unit is essentially sensitive to a different primary color region of the visible spectrum and contains a nondiffusible photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nondiifusible dye essentially complementary in color to the sensitivity of the layer in which it is incorporated and (2) an auxiliary sound recording silver halide emulsion layer containing silver halide of 0.05 micron to 0.2 micron grain size which does not form an image upon imageforming exposure of said picture recording units, said auxiliary layer containing a colorless nondiffusible photographic color coupler which reacts with oxidized aromatic primary amine color developing agent which comprises (A) developing a picture record in the picture area comprising silver and a nondiifusible dye and developing a sound track recording comprising silver, (B) contacting said auxiliary layer with 1-(3-nonanamidophenyl)-5-mercaptotetrazole contained in an aqueous ballasted silver bleach inhibitor bath comprised of 0.4 g./ liter l-(3-nonanamidophenyl) 5 mercaptotetrazole and having a pH of 12.1 to adsorb said l-(3-nonanamidophenyl)-5-mercaptotetrazole onto at least the silver of the auxiliary layer and (C) removing the bleachable silver images remaining in the picture areas after step (B) and the residual silver halide.

38. A photographic color film comprising a transparent support having coated thereon, on one surface in order (1) three picture recording photographic color-forming units, each unit comprising at least one silver halide emulsion layer, which are so disposed and sensitized that each said unit is essentially sensitive to a different primary color region of the visible spectrum and cotains at least one nondiffusing photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a dye essentially complementary in color to one of the primary color regions of the visible spectrum and (2) an auxiliary sound recording silver halide emulsion layer which does not form an image upon imageforming exposure of said picture recording units, said auxiliary layer containing a colorless nondiffusible compound which reacts with oxidized aromatic primary amine color developing agent and which decreases the rate of diffusion of a ballasted silver bleach inhibitor through said auxiliary layer.

39. A photographic color film of claim 38 wherein said compound in said auxiliary layer is a photographic color coupler.

40. A photographic color film of claim 39 wherein said nondiffusing photographic color coupler in each of said picture recording units forms a dye essentially complemen- 38 tary in color to the sensitivity of the emulsion in which it is incorporated.

41. A photographic color film comprising a transparent support having coated thereon, on one surface in order, (1) a picture recording photographic color-forming unit comprising at least one silver halide emulsion layer sensitive primarily to the blue region of the visible spectrum and containing at least one nondiflusing photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nondiffusing yellow dye, (2) a picture recording photographic color-forming unit comprising at least one silver halide emulsion layer sensitive primarily to the red re- 1 gion of the visible spectrum and containing at least one nondifi'using photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nondiffusing cyan dye, (3) a picture recording photographic color-forming unit comprising at least one silver halide emulsion layer sensitive primarily to the green region of the visible spectrum and containing at least one nondiifusing photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nondiflusing magenta dye and (4) an auxiliary sound recording silver halide emulsion layer which does not form an image upon image-forming exposure of the picture recording units, said auxiliary layer containing a colorless nondiffusible compound which reacts with oxidized aromatic primary amine color developing agent and which decreases the rate of diffusion of a silver bleach inhibitor through said auxiliary layer.

42. A photographic color film of claim 41 wherein said compound of said auxiliary layer is a photographic color coupler.

43. A photographic color film of claim 42 wherein said silver halide of said auxiliary layer has a grain size of 0.05 micron to 0.2 micron.

44. A photographic color film comprising a transparent support having coated thereon, on one surface in order (1) a picture recording photographic image-forming unit comprising at least one silver halide emulsion layer sensitive primarily to the red region of the visible spectrum, (2) a picture recording photographic unit comprising at least one silver halide emulsion layer sensitive primarily to the green region of the visible spectrum, (3) a yellow filter layer, (4) a picture recording photographic unit comprising at least one silver halide emusion layer sensitive primarily to the blue region of the visible spectrum and (5) an auxiliary sound recording silver halide emulsion layer which does not form an image upon imageforming exposure of said picture recording units.

45. A photographic color film of claim 44 wherein said auxiliary layer contains a colorless nondiffusible compound which reacts with oxidized aromatic primary amine color developing agent and which decreases the rate of diffusion of a silver bleach inhibitor through said auxiliary layer.

46. A photographic color film of claim 45 wherein said compound is a photographic color coupler.

47. A photographic color film of claim 46 wherein said unit (1) contains a nondiffusing photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nonditfusing cyan dye, said unit (2) contains a nondiifusing photographic color coupler which reacts with oxidized aromatic primary amine developing agent to form a nondifi'using magenta dye and said unit (4) contains a nondiffusing photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nondifi'using yellow dye.

48. In the process of producing a picture record and an auxiliary silver record in a photographic element exposed to picture and auxiliary exposures, said element comprising a support having coated on one side of the support, in order:

(1) a picture-recording photographic image-recording

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3940271 *Feb 4, 1974Feb 24, 1976Fuji Photo Film Co., Ltd.Color photographic light-sensitive material
US4208210 *Mar 24, 1977Jun 17, 1980Fuji Photo Film Co., Ltd.Process for forming an optical soundtrack
US4216284 *Sep 29, 1977Aug 5, 1980Fuji Photo Film Co., Ltd.Color photographic light-sensitive material
US4269923 *Jan 22, 1980May 26, 1981Agfa-Gevaert N.V.Photographic imaging process and materials suitable therefor
US5753402 *Jul 15, 1996May 19, 1998Eastman Kodak CompanyMethod for recording and processing motion picture film soundtrack
US7914977Sep 28, 2005Mar 29, 2011Fujifilm CorporationSilver halide color photosensitive material and method of processing the same
US20080286702 *Sep 28, 2005Nov 20, 2008Fujifilm CorporationSilver Halide Color Photosensitive Material and Method of Processing the Same
EP0014494A1 *Jan 16, 1980Aug 20, 1980AGFA-GEVAERT naamloze vennootschapPhotographic imaging process and materials suitable therefor
EP0252550A1 *Jun 24, 1987Jan 13, 1988AGFA-GEVAERT naamloze vennootschapColour photographic motion picture projection film element
EP0779542A2Oct 16, 1996Jun 18, 1997Eastman Kodak CompanySound recording film
Classifications
U.S. Classification430/140, 430/403, 430/934
International ClassificationG03C7/24
Cooperative ClassificationG03C7/24, Y10S430/135
European ClassificationG03C7/24