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Publication numberUS3620745 A
Publication typeGrant
Publication dateNov 16, 1971
Filing dateApr 1, 1968
Priority dateApr 1, 1968
Publication numberUS 3620745 A, US 3620745A, US-A-3620745, US3620745 A, US3620745A
InventorsMerrill W Seymour
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Color photographic silver halide emulsions of different developing speed one layer having a dir coupler
US 3620745 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent [72] lnventor Merrill W. Seymour East Orleans, Mass. [21] Appl. No 717,924 [22] Filed Apr. 1, 1968 [45] Patented Nov. 16, 1971 [73] Assignee Eastman Kodak Company Rochester, N.Y.

[54] COLOR PHOTOGRAPHIC SILVER HALIDE EMULSIONS OF DIFFERENT DEVELOPING SPEED ONE LAYER HAVING A DIR COUPLER 19 Claims, No Drawings [52] US. Cl 96/68, 96/100, 96/74, 96/55, 96/66.3, 96/56.5 [51] Int. Cl G03c 1/76 [50] Field of Search 96/68, 74, 100

[56] References Cited UNlTED STATES PATENTS 3,140,179 7/1964 Russell 96/68 3,148,062 9/1964 Whitmore et al. 96/100 X 3,227,551 l/l966 Barr et al 96/74 X Primary Examiner-Norman G. Torchin Assistant Examinerlohn L. Goodrow Attorneys-William H. J. Kline, James R Frederick and Ray Carter Livermore ABSTRACT: A photographic material comprising a support coated with (l) a first light-sensitive layer containing a silver halide emulsion preferably a coarse grain emulsion either alone or with a colorless nondiffusing color-forming coupler that forms a nondiffusible dye upon color development and (2) a second light-sensitive layer containing a finer grain rapidly developing silver halide emulsion and a colorless non diffusing development inhibitor releasing coupler that forms a dye and a diffusible development inhibitor upon color development by a primary aromatic amine color developing agent, is used advantageously to record a first light image in the first layer and a second light image in the second layer and produce upon color development an image reproduction of the second light image in the second layer and only produce a visible image reproduction of the first light image in the first layer that is not directly under (or over) the image reproduction in the first layer, such that the two image reproductions are vividly different.

COLOR PHOTOGRAPIIIC SILVER HALIDE EMULSIONS OF DIFFERENT DEVELOPING SPEED ONE LAYER HAVING A DIR COUPLER materials containing differently sensitized silver halide emulsion layers that contain incorporated color-forming couplers which upon color development form differently colored dye images that combine to form the resulting color reproduction. Usually the red-sensitized silver halide emulsion layer contains a phenolic or naphtholic dye-forming coupler, the green-sensitized silver halide emulsion layer contains a magenta-forming pyrazolone coupler and the blue-sensitive silver halide emulsion layer contains an open-chain yellow dye-forming coupler. In these photographic elements great care is exercised in adjusting the speeds and sensitometric characteristics of the three differently sensitized emulsion layers so that the resulting dye images will have ideally the same relationship of dye density to exposure. This is necessary so that a gray scale can be reproduced and also so that a colored image will reproduce with the same color regardless of the exposure given providing it is within the sensitivity range of the photographic film. It is also known in color photography to use twoequivalent couplers which require only one-half the amount of silver halide development to produce a given amount of dye that is required by four-equivalent couplers. It is also known to use development inhibitor-releasing (DIR) couplers, such as are described in Whitmore et al. US. Pat. No. 3,148,062, issued Sept. 8, 1964, and Barr et al. US. Pat. No. 3,227,554, issued Jan. 4, 1966.

ln photographic recording systems, it is often desired to record two separate images and be able to study them in superposed relationship. When one of the two images is made up of small and especially minute image areas, such as, fine lines, small dots, etc., they may be difficult to distinguish from the second image. It is known to reproduce two such images in different colors, however, even then the fine line or dots may be very difficult to distinguish in areas where a second image reproduction underlies them because of the degradation or darkening of the color of the fine line or dot by the color of the underlying image.

For aerial reconnaissance, it is desired to record a light image of a map emitted from a phosphor-coated radar screen from side-looking radar (referred to hereinafter as SLR) and to simultaneously record a second light image emitted from a phosphorcoated radar screen showing moving target information (referred to hereinafter as MTl) from the same area represented or shown by the map. The radar signals received by the radar scope providing MTI are electronically filtered so that the radar scope shows only images of moving objects. In order for the processed picture to serve the purpose for which they are intended, they must be available quickly and be combined in such a way that the images are properly registered. A photographic material and process is desired for simultaneous recording of the SLR and MTI images and then processing them so that even when the MTI image reproductions are very small, they are vividly distinct from the SLR map image reproduction.

It is an object of my invention to provide a novel light-sensitive photographic material and process capable of recording a plurality of images and reproducing them so that even very minute details in the reproduction of the images are vividly discernible.

Another object of my invention is to provide a novel lightsensitive photographic material and process for recording and reproducing images of very small moving targets so they are very readily discernible against the underlying image of a sidelooking radar map.

These and still other objects will be apparent from consideration of the following specification and claims.

These and still other objects are accomplished according to my invention by the preparation and use of my novel photographic recording materials. In the simplest form, one embodi ment of my photographic recording material comprises a support coated with a first light-sensitive hydrophilic colloid layer containing a silver halide emulsion, preferably a coarse-grain emulsion sensitive to at least one region of the actinic spectrum (i.e., light of from about 5 to about 1,200 .1. which silver halide emulsions will record) either alone or with a nondiffusing color-forming coupler preferably colorless that reacts with an oxidized primary aromatic amine color developer and forms a nondiffusing dye image, and a second light-sensitive hydrophilic colloid layer containing a finer grained rapidly developing silver halide emulsion sensitive to at least one region of the actinic spectrum that is different from the region(s) of the actinic spectrum to which the said silver halide emulsion in the first light-sensitive layer is sensitive and contiguous to silver halide grains of the emulsion in the second light-sensitive layer, a colorless nondiffusing development inhibitor releasing (DIR) coupler that forms a dye and a diffusible development inhibitor upon color development by a primary aromatic amine color developing agent. Preferably the DIR coupler forms a nondiffusing dye, however, it can be a diffusible dye when the first light-sensitive layer forms a dye image. During color development, the finer grained rapidly developing silver halide emulsion is substantially completely developed and the image-wise pattern of development inhibiting agent has diffused into the coarser grained silver halide emulsion layer before it starts to develop so the development inhibiting agent very substantially, if not completely, inhibits development of the silver halide emulsion in the first light-sensitive layer directly under (or over) the silver and dye image formed in the second light-sensitive layer. Although the development inhibitor substantially inhibits development of the silver halide emulsion in areas of the first light-sensitive layer under (or over) the silver and dye image formed in the second light-sensitive layer, the development inhibitor has substantially no inhibiting effect on the development of the silver halide in the second light-sensitive layer. This insures a good silver and dye image in the second lightsensitive layer with essentially no image, if any, being formed in the first light-sensitive layer directly under (or over) it so that the image in the second light-sensitive layer is very readily discernible from images in the first light-sensitive layer. When a colorless nondiffusible color-forming coupler is used in the first light-sensitive hydrophilic colloid layer, it is chosen so that it forms a dye having a different color from the dye formed in the second lightsensitive layer by color development of the DIR coupler. This embodiment of my photographic recording material is used to advantage to record two separate differently colored images by exposure through one side, e.g., to record an image ofa SLR map which is optically combined and registered with the radar information showing MTl so that the film is exposed in a single step with the SLR map image recorded in the first light-sensitive layer and the radar information showing MTl recorded in the second lightsensitive layer.

In the simplest form of another embodiment of my photographic recording material, the first light-sensitive hydrophilic colloid layer described previously, is separated from the second light-sensitive hydrophilic colloid layer described previously by a hydrophilic colloid layer containing a bleachable light-absorbing filter that will absorb the exposing image light. These layers are coated on a transparent support and the exposure of the one image, e.g., SLR map image is made through the transparent support while exposure of the second image, e.g., the radar information showing M'll is made directly onto the top layer in such a way that the two images when developed will be in register. Since a lightabsorbing filter layer is used to confine the exposure of each of the two light-sensitive layers to the respective light image each is supposed to record in this embodiment, the two emulsions need not be spectrally sensitized or they can be advantageously spectrally sensitized in any way desired including identical spectral sensitization.

In another embodiment of my invention a support is coated with (l a first hydrophilic colloid layer containing a first finer grained rapidly developing silver halide emulsion sensitive to at least one region of the actinic spectrum and contiguous to the silver halide grains in this emulsion a first colorless nondiffusible development inhibitor-releasing coupler that reacts with oxidized primary aromatic amine color developing agent to form a first nondiffusible dye and release a diffusible development inhibitor, (2) a second hydrophilic colloid layer containing a coarse-grain slower developing emulsion that is sensitive to at least one region of the actinic spectrum that is different than for the emulsion in (l) and contiguous to the silver halide grains in the said coarse-grain emulsion, a colorless nondiffusing coupler which reacts with oxidized primary aromatic amine color developer to form a second nondiffusing dye having a color that is different from that formed by reaction of the said coupler in (l), and (3) a hydrophilic colloid layer containing a second finer grained rapidly developing silver halide emulsion sensitive to at least one region of the actinic spectrum that is different from the regions that the silver halide emulsions in (l) and (2) are sensitive to, and contiguous to the silver halide grains in the said second finer grain emulsion, a second colorless nondiffusing development inhibitor-releasing coupler that reacts with oxidized primary aromatic amine color developing agent to form a third nondiffusing dye having a color that is different from the dyes formed by the reaction of the said couplers in (1) and in (2). Upon development with a primary aromatic amine color developer, exposed silver halide in the first and third layers is very rapidly developed to the respective silver and dye images with the release of development inhibitor in each of these layers which diffuse into the said second layer and substantially inhibits the development of any latent image in that layer that corresponds to a dye image developed in either or both the first and third layers.

in another embodiment, variations of the above embodiments are used in which two or more of the sets of light-sensitive layers described above are coated on a single support. The different silver halide emulsions in such an element are advantageously spectrally sensitized so that each one responds to an appropriate range of wavelengths in the actinic spectrum that is different from those to which the others respond. Similarly the couplers are advantageously chosen so that they produce upon color development differently colored dyes. Preferablydyes are chosen which are as different as possible, however when more than 3 or 4 different dye images are needed the differences will be smaller and it is advantageous to select dyes which have sharply cutting absorption curves with A max values that are distinctly different from those of the other dyes used in the element. Where desired in such elements to prevent development inhibitor released in one set of the light-sensitive layers from affecting development in a layer of another set of light-sensitive layers, it is advantageous to coat an interlayer containing colloidal silver, silver halide or other material that will prevent diffusion of the development inhibitor.

In the embodiments of my invention, described above, it is advantageous but not necessary to include between the lightsensitive layers a nonlight-sensitive hydrophilic colloid layer containing a scavenger for oxidized color developing agent to prevent any oxidized color developing agent formed in the second light-sensitive layer from wandering into the first lightsensitive layer. In the embodiment where a light-absorbing filter layer is placed between the first and second light-sensitive layers, the scavenging agent is advantageously included in this layers.

In another embodiment of my invention a support is coated with a first light-sensitive hydrophilic colloid layer containing a coarse-grain silver halide emulsion sensitive to one region of the actinic spectrum with or without a colorless nondiffusing coupler that reacts with oxidized primary aromatic amine color developer to produce a first dye image and a second light-sensitive hydrophilic colloid layer containing a dispersion of a plurality of differently sensitized packets each containing a fine grain rapidly developing silver halide emulsion and contiguous to the silver halide grains in the packet an uncolored nondiffusing development inhibitor-releasing coupler which reacts with oxidized primary aromatic amine color developing agent to form a nondiffusing dye. Packets sensitive to one region of the actinic spectrum are designed to produce a dye image that has a different color than the dye images produced by packets sensitized to other regions.

My exposed photographic materials are developed by contacting the photographic element with an aqueous alkaline color developer solution containing a primary aromatic amine color developing agent which upon penetrating the hydrophilic colloid layers rapidly produces a silver and a dye image of the latent image in the finer grain, rapidly developing silver halide emulsion and liberates the development inhibiting agent in an image-wise pattern corresponding to the silver and dye image formed. The image-wise pattern of development inhibiting agent and exhausted color developer diffuse into the next emulsion layer to inhibit development of the latent image in the coarse-grain silver halide emulsion in areas corresponding to the developed image in the other layer, while the unused color developing agent develops the other parts of the latent image into a visible image comprising a silver image and a dye image (when a color-forming coupler has been incorporated in this layer). The development inhibiting effect in the coarse grain slower developing silver halide emulsion layer often extends to an area slightly larger than the silver and dye image in the finer grain rapidly developing layer so this image is encircled by a narrow, clear area in which there is no silver or dye image in the coarse-grain image layer. This effect is very advantageous since it still further sets out one image against the other image. In my photographic materials which contain couplers in all the light-sensitive layers, the silver images may be removed from the film by treatment with an oxidizing agent such as a solution of potassium ferricyanide or cupric chloride followed by hypo solution which removes both oxidized silver and the undeveloped silver halide. This treatment leaves only the dye images in the film, a bright dye image of one color in the top layer superposed upon a differently colored image reproduced in the bottom layer with substantially no degradation of the brightly colored image in the top layer by an underlying image in the bottom layer. As was mentioned previously. the top layer images are often encircled with a clear area in the bottom layer even in areas where a latent image had been previously produced in that layer.

For the sake of simpler and more rapid processing of the film, it may be advantageous to omit the removal of the silver images and the undeveloped silver halide possibly with the substitution of a stabilizing solution, such as thiourea, in place of bleaching and fixing as was described above. No bleaching step could be used, of course, for the processing of my photographic elements which do not use a color-forming coupler in both layers. This procedure will leave a silver image in one layer and a silver and dye image in the other layer. Consequently, it is desirable to use in the top layer a fine-grain emulsion that will produce a fine grain silver image that will be as transparent as possible. When the dye image formed in the top layer is magenta colored, it is preferable to use a fine grain silver halide emulsion in the top layer that will produce a warm tone silver image approaching the color of the dye image in the same layer while the emulsion in the bottom layer would preferably be one producing a silver image of :1 cold gray tone.

Any of the usual supports used in photographic materials can be used to advantage in making my photographic elements including such typical supports as cellulose nitrate film. cellulose acetate film, polyvinyl acetal film, polystyrene film. polyterephthalate film, polyethylene film, polypropylene film. polyethylene-coated paper, paper, glass and others.

Any of the hydrophilic colloids used in the preparation of photographic elements are used to advantage in preparing the layers of my photographic materials. lllustrative examples include gelatin, colloidal albumin, cellulose derivatives or synthetic resins, such as, polyvinyl alcohol, etc.

The silver halide emulsion, preferably of camera speed, used in the first light-sensitive layer can be any silver halide emulsion used in photography, e.g., silver chlorobromide, silver bromoiodide silver chlorobromoiodide, etc., preferably silver bromoiodide and an emulsion that is coarser grained and slower developing than the emulsion used in the second light-sensitive layer. Silver chloride when present usually comprises a smaller percent of the silver halide than in the second layer.

The silver halide emulsion used in the second light-sensitive layer is advantageously a finer grained rapidly developing silver halide emulsion, e.g., silver chlorobromide, silver chlorobromoiodide, etc., and is preferably of camera speed.

My emulsions are unfogged negative acting and when my elements containing them are developed in DK 50 developer solution for 5 minutes at 68 F. followed by fixing in conventional hypo fix bath, washing and drying, they produce a density in unexposed areas of not more than about 0.1 density units.

My camera speed emulsions have A.S.A. exposure indices of at least 10. The emulsions which are spectrally sensitized in my photographic elements are advantageously spectrally sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Pat. Nos. 1,846,301 and 1,846,302; and 1,942,854; White U.S. Pat. No. 1,990,507; Brooker and White U.S. Pat. Nos. 2,112,140; 2,165,338; 2,493,747; and 2,739,964; Broolter et al. U.S. Pat. No. 2,493,748, issued Jan. 10, 1950; Sprague U.S. Pat. Nos. 2,503,776, issued Apr. 11, 1950, and 2,519,001, issued Aug. 15, 1950; Heseltine et a1. U.S. Pat. No. 2,666,761, issued Jan. 19, 1954; Heseltine U.S. Pat. No. 2,734,990, issued Feb. 14, 1956; VanLare U.S. Pat. No. 2,739,149, issued Mar. 20, 1956; and Kodak Limited British Pat. No. 450,958; accepted July 15, 1936.

The photographic silver halide emulsions and other layers on my photographic elements can contain any of the addenda generally utilized in photographic elements including speed increasing materials, antifoggants, coating aids, gelatin hardeners, plasticizers, ultraviolet absorbers and the like.

Any of the conventional four-equivalent or two-equivalent nondiffusing couplers used in photographic elements are used to advantage in the first light-sensitive layer of my photographic materials, however, it is preferred to use the twoequivalent couplers (but not including DlR couplers). My couplers are all colorless.

The open-chain active methylene containing couplers used to advantage include the cyanoacetyl couplers, such as the cyanoacetylcoumarone couplers, the cyanoacetylbenzoyl couplers, the heterocyclicacetonitrile couplers, etc.), the open-chain ketomethylene couplers, such as, the acylacetyl couplers (e.g., the acylacetanilide couplers, the acylacetamide couplers, etc.). The acylacetanilide couplers include the alkoylacetanilide couplers, the aroylacetanilide couplers, the pivalylacetanilide couplers, etc. The acylacetamide couplers include the alkoylacetamide couplers, the aroylacetamide couplers, the pivalylacetarnide couplers, etc.

These four-equivalent open-chain couplers include those represented advantageously by the formula:

wherein R represents an alkyl group (substituted or not), an aromatic group (substituted or not), a heterocyclic group (substituted or not), etc.; and X represents the cyano group, a

Typical foubequivalent yellow-forming couplers include the following:

1. N-amyl-p-benzoylacetaminobenzenesulfonate 2. N-(4-anisoylacetaminobenzenesulfonyl)-N-benzy1-mtoluidine 3. N-(4-benzoylacetaminobenzenesulfonyl)-N-benzylaniline 4. w-(p-benzoylbenzoyl)acetanilide 5. w-benzoyl-p-sec.-amylacetanilide 6. N,N'-di(w-benzoylacetyl)-p-phenylenediamine 7. ai3-[a-(2,4-di-tert-amylphenoxy)butyramido]-benz0yl }-2-methoxyacetanilide 8. 4,4-di-(acetoacetamino)-3,3 -dimethyldiphenyl 9. p,p'-di-(acetoacetamino)diphenylmethane l0. nonyl-p-benzoylacetaminobenzenesulfonate 1 1. N-phenyl-N-(p-acetoacetaminophenyl)urea l2. N-propyl-p-benzoylacetaminobenzenesulfonate acetoacetpiperidide l3. N(w-benzoylacetyl) 1 ,2,3 ,S-tetrahydroquinoline 14. N(m-benzoylacetyl)morpholine The two-equivalent yellow-forming couplers are derived from the general types of parent four-equivalent couplers by replacing one of the two hydrogens on the alpha-carbon (i.e., methylene) with any nonchromophoric coupling off group including groups such as the fluorine atom, the chlorine atom, an acyloxy group, a cyclooxy group and a thiocyano group. Typical two-equivalent couplers used to advantage included the alpha-fiuoro couplers of U.S. Pat. No. 3,277,155, the achloro couplers of U.S. Pat. No. 2,778,658, the a-thiocyano couplers of U.S. Pat. 3,253,924, the a-acyloxy couplers of Loria U.S. Pat. application Ser. No. 477,353, filed July 26, 1965, the a-cyclooxy couplers of Loria U.S. Pat. application Ser. No. 469,887, now U.S. Pat. No. 3,408,194 filed July 6, 1965, and the aalkoxy couplers of the type shown in Whitmore et al. U.S. Pat. No. 3,227,550.

The two-equivalent open-chain yellowiorming couplers include those represented by the formula:

wherein R and X are as described previously; Y is a coupling off group, such as, the chlorine atom, the fluorine atom, the thiocyano group, an acyloxy group leg, an alkoyloxy group (substituted or not), an aroyloxy group (substituted or not), a heterocycloyloxy group (substituted or not), etc. in which the groups are substituted with a wide variety of well-known groups and also a group in which R and X are as described previously], and a cyclooxy group [e.g., an aryloxy group (e.g., a phenoxy group), a naphthoxy group, a heterocycloxy group (e.g., a pyridinyloxy group, a tetrahydropyranyloxy group, a tetrahydroquinolyloxy group, etc.)], an alkoxy group, an alkthio group and an arylthio group in which these groups are advantageously substituted with a wide variety of well'known groups and also a group in which R and X are as defined previously.

Typical illustrative examples of two-equivalent yellow forming couplers include the following:

1. 4-(01-2methoxybenzoyl-a-chloroacetamido)-3"-(4" tert.-amylphenoxy )benzanilide 2. a-o-methoxybenzoyl-a-chloro-4-[a-(2 4-di-tertamylphenoxy)-n-butyramido] -acetanilide 3. a-{3-[a-(2,4-di-tert-amylphenoxy)butyramido1benzoylla-fluoro-2-methoxyacetanilide 4. a-fluoro-a-pivalyl-S-[ -(2,4-di-tert-amylphenoxy lbu tyramido]-2-chloroacetanilide 5. a-acetoxy-a- 3-[-y-( 2,4-di-tert-amylphenoxy )butyramidolbenzoyl Z-methoxyacetanilide 6. a-benzoyl-a-[a-(2,4-di-n-amylphenxy)acetoxy1-2- methoxyacetanilide 7. a-pivalyl-a-stearoyloxyt-sulfamylacetanilide 8. a-pivalyl-a-[a-(3-pentadecylphenoxy)acetoxy]-3,5-

dicarboxyacetanilide 9. a-acetoxya- {3-[a-(2,4-di-tert-arnylphenoxy)butyramidolbenzoyl}-2-methoxyacetanilide l0. a-(3-dodecanamidobenzoyl)-a-octanoyloxy-2-methoxyacetanilide l l. a- {3-[y-(2,4-di-tert-amylphenoxy)butyramiclolbenzoyll -a(4-nitrophenoxy )-2-methoxyacetanilide l2. a-[4-(N-methyl-N-octadecylsulfamyl)phenoxy] apivalyl-4-sulfoacetanilide potassium salt 13. a-pivalyl-oz-(4-sulfophenoxy-4-N-methyl-N-ocatadecylsulfamyl)acetanilide potassium salt l4. a-[4-( 4-hydroxyphenylsulfonyl )phenoxy ]-a-pivalyl-2- chloro-S-[ -(2,4-di-tert-amylphenoxy )butyramido Iacetanilide 15. 4,4'-bis[a-pivalyl-a-{ 2-chloro-5-[ -(2,4-di-tertamylphenoxy)butyramidolphenylcarbamyl} methoxy]- diphenylsulfone 7 l6. a-benzoyl-a-thiocyanoacetanilide Any of the well-known one-substituted and/or three-substituted S-pyrazolone couplers that are incorporated in photographic emulsion layers are used to advantage.

The four-equivalent magenta-forming couplers used according to my invention includes those having the formula:

wherein R is as described previously and R represents a group such as an alkyl group, a substituted carbarnyl group, an amino group (substituted or not with one or two alkyl groups and/or one or two aryl groups), a substituted amido group e.g., a benzamido group (substituted or not), an alkamido group (substituted or not), etc. The R and/or R groups are advantageously substituted with any of the well-known substituent groups used in color-forming couplers including ballasting groups to render the couplers nondiffusible in hydrophilic colloid layers, and solubilizing groups.

Typical illustrative examples of four-equivalent magentaforming couplers include the following:

I l-p-sec.-amylphenyl-3-n-amyl-5-pyrazolone 2. 2-cyanoacetyl-5-p-sec.-amylbenzoylamino)coumarone 3. Z-cyanoacetylcoumarone-S-(N-n-amyl-p-tert.-amylsulfanilide) 4. 2-cyanoacetylcoumarone-S-sulfon-N-n-butylanilide 5. 2-cyanoacetyl-5-benzoylamino-coumarone 6. 2-cyanoacetylcoumarone-5-sulfondimethylamide 7. 2-cyanoacetylcoumarone 5-sulfon-N-methylanilide 8. 2cyanoacetylcoumarone-5-(N-y phenylpropyl(-p-tert.-

amylsulfonanilide 9. l-p-laurylphenyl-3-methyl-5-pyrazolone l0. l-fl-naphthyl-3 -amyl-5 -pyrazolone l-p-nitrophenyl-3n-amyl-5-pyrazolone l-p-phenoxyphenyl-3-n-amyl-5-pyrazolone l-phenyl-3-n-amyl-5-pyrazolone 1,4-phenylene bis-3-( l-phenyl-S -pyrazolone) l-phenyl-3-acetylamino-5-pyrazolone l-phenyl-3-n-valerylamino-5-pyrazolone l-phenyl-3-chloroacetylamino-S-pyrazolone l-phenyl-3-benzoylamino-5-pyrazolone l-phenyl-3-(m-aminobenzoyl)amino-S-pyrazolone l-phenyl-3-(p-sec.-amylbenzoylamino)-5-pyrazolone 1-phenyl-3-diamylbenzoylamino-S-pyrazolone l-phenyl-3-fl-naphthoylamino-5-pyrazolone l-phenyl-3-phenylcarbamylamino-5-pyrazolone 1-phenyl-3-palmitylamino-S-pyrazolone l-phenyl-3-benzenesulfonylamino-5-pyrazolone 26. l-(p-phenoxyphenyl)-3-( p-tert-amyloxybenzoyl)amino- 5-pyrazolone 27. 1-(2',4',6'-trichlorophenyl)-3-benzamido-S-pyrazolone 28. l-(2,4',6'-tribromophenyl)-3-phenylacetamido-5- pyrazolone 29. l-(2',4-dichlorophenyl)-3-[3"-(2',4"'-ditertamylphenoxyacetamido)benzamidoih-S-pyrazolone 30. l-(2',4',6'-trichlorophenyl)-3-[3"-(2",4"-di-tert.-

amylphenoxyacetamido)benzamidoih-S-pyrazolone l-(2,4',6'-trichlorophenyl)-3-[B-2"',4"-di-tert.- amylphenoxy)-propionamido]-5-pyrazolone 32. l-(2',5'-dichloro)-3-[3"-(4"-tert.-amylphenoxy)benzamido]-5-pyrazolone 33. l-(2',4',6-tribromophenyl)-3-[3"-(4'-tert.-

amylphenoxy)-benzamidol-5-pyrazolone 34. l-(2',5-dichlorophenyl)-3-[3"-(2",4"-di-tertamylphenoxyacetamido)benzamidoih-S-pyrazolone The two-equivalent couplers are derived from the fourequivalent parent couplers by replacing one of the hydrogens on the carbon in the 4-position of the pyrazolone ring with a nonchromophoric coupling off group. Examples of coupling off groups used to advantage in two-equivolent magenta-forming couplers are the thiocyano group illustrated by the couplers in Loria U.S. Pat. No. 3,252,924 and the acyloxy group containing two-equivolent magenta-forming couplers of Loria U.S. Pat. No. 3,31 1,476. The other coupling off groups include acyloxy, aryloxy, alkoxy such as are shown in Whitmore et a1. U.S. Pat. No. 3,227,550, the chlorine atom, the fluorine atom, and the sulfo group.

The two-equivalent magenta-forming couplers used accord ing to my invention include those having the formula:

wherein R and R are as defined previously; and Y represents a coupling off group, such as, the thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group, the chlorine atom, the fluorine atom, the sulfo group, etc.

Typical illustrative examples of two-equivalent magentaforming couplers include the following:

1. 1-(2,4,6-trichlorophenyl)-3-(4-nitroanilino )-4- stearoyloxy-S-pyrazolone 2. l-(2,4,6-trichlorophenyl)-3-{3-[a-(2,4-di-tertamylphenoxy)-acetamido]benzamido}-4-acetoxy-5- pyrazolone 3. l-(2,4,6-trichlorophenyU-3-pentadecyl-4-thiocyano-5- pyrazolone 4. l-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-tert-amylphenoxyacetamido)benzamido]-4-thiocyano-S-pyrazolone 5. l-(p-tert-butylphenoxyphenyl)-3-a-(p-tert'butyl-phenoxy)-propionamido-4-thiocyano-5-pyrazolone 6. 1-(2,4,6-trichlorophenyl)-3-pentadecyl-4-sulfo-5 pyrazolone 7. 1-(2,4,6-trichlorophenyl)-3-pentadecyl-4-chloro-5- pyrazolone 8. l-[4-(3,S-dicarboxylbenzamido)phenyl}-3-ethoxy-4-(3- octadecylcarbamylphenylthio)-5-pyrazolone Any of the well-known four-equivalent phenolic and naphtholic cyan-forming couplers can be used to advantage in my photographic materials.

The four-equivalent cyan-forming couplers used according to my invention include those having the formulas:

0H VI.

and

wherein R represents hydrogen, an alkyl group, an aryl group, a heterocyclic group, an amino group (e.g., amino, alkylamino, arylamino, heterocyclic amino, etc.), a substituted carbonamido group (e.g., an alkylcarbonamido group, an arylcarbonamido group, and a heterocycliccarbonamido group), a substituted sulfonamido group (e.g., an alkylsulfonamido group, an arylsulfonamido group, a heterocyclicsulfonamido group, etc.), a substituted sulfamyl group (e.g., an alkylsulfamyl group, an arylsulfamyl group, a heterocyclic sulfamyl group, etc.), a substituted carbamyl group (e.g., an alkylcar bamyl group, an arylcarbamyl group, a heterocyclic carbamyl group, etc.), a halogen atom (e.g., chlorine, bromine, etc.) etc.; and R R and R each represent any of the groups represented by R and in addition an alkoxy group, etc., R R, R and R are advantageously further substituted by any of the ballasting groups well known in the art.

Typical four-equivalent cyan-forming couplers include the following illustrative examples:

l. 5-(p-amylphenoxybenzenesulfonamino l -naphthol 2. 5-(n-benzyl-N-n-valerylamino)- l -naphthl 3. S-caproylamino-l-naphthol 4. 2-chloro-5-(N-n-valeryl-N-p-isopropylbenzylamino)-lnaphthol 5. 2-chloro-5 -palmitylaminol -naphthol 6. -diphenylethersulfonamido-l -naphthol 7. l-hydroxy-2-(N-isoamyl-N-phenyl)naphthamide 8. S-hydroxyl -a-naphtholl ,2,3 ,4-tetrahydroquinoline 9. l-naphthol-S-sulfo-cyclohexylamide l0. S-phenoxyacetaminol -naphthol l l. Monochlor-5-(N-yphenylpropyl-N-p-sec.-amylbenzoyl-amino)-l-naphthol l2. 2-benzoylamino-3,S-dimethylphenol l 3. 2-a-(p-tert-amylphenoxy)-n-butyrylamino-5- methylphenol 14. l -hydroxy-N-[cz-(2,4-di-tert.-amylphenoxy)butyl1-2- naphthamide l5. 2-( 4-tert.-amyl-3 -phenoxybenzoylamino )-3 ,5-

dimethylphenol l6. 2-(4-tert.-amyl-3-phenoxybenzoylamino)phenol l7. 2-[a-(4-tert.-butylphenoxy)propionylamino]phenol l8. 2-[N-methyl-N-(4-tert.-amyl-3-phenoxybenzoylamino) [phenol l9. 2-a-(4-tert.-amylphenoxy)butyrylarnino-l-phenol 20. 2-(4-tert.-amyl-3-phenoxybenzoylamino)-3,5-

dimethylphenol 21. 2-[a-(4-tert.-amylphenoxy)-n-butyrylamino]-5-methylpehnol 22. 3-(4-tert.-amyl-3'-phenoxybenzoylamino)phenol 23. 2-[a-(4-tert.-amylphenoxy)-n-butyrylamino1-6- chlorophenol 24. 3-[a-(4-tert.-amylphenoxy)-n-butyrylamino]-5- chlorophenol 25. 5-benzene sulfonamido-l-naphthol 26. 2-chloro-5-benzenesulfonamidol -naphthol 27. 5-( l,2,3,4-tetrahydronaphthalene-6-sulfonamido l naphthol 28. 2-chloro-5-(4-bromodiphenyl-4-sulfonamido l naphthol Any of the well-known two-equivalent cyan-forming couplers known in the art for incorporation in photographic layers may be used to advantage. Usually the two-equivalent couplers are derived from the corresponding four-equivalent couplers by substituting a nonchromophoric coupling off group on the carbon in the 4-position of the phenolic or naphtholic ring. Included among the coupling off groups are the acyloxy group illustrated by the 4-acyloxyphenols and 4- acyloxynapthols of Loria U.S. Pat. No. 3,31 l,476, issued Mar. 28, 1967, the cyclooxy group illustrated by the 4-cyclooxy naphthols of Loria U.S. Pat. application Ser. No 483,807, now U.S. Pat. No. 3,476,563, filed Aug. 30, 1965, the thiocyano group illustrated by the 4-thiophenols and 4- thionaphthols of Loria U.S. Pat. No. 3,253,294, the cyclic imido groups as illustrated by the 4-cyclic imido derivatives of VII. OH VIII. OH

and

wherein R R", R and R are as defined previously; Y represents the groups previously defined for Y but does not represent an aryloxy group; Y- represents the groups previously defined for Y and also includes a cyclic imido group (e.g., a maleimido group, a succinimido group, a l,2-dicarboximide group, a phthalimido group, etc.).

Typical examples of two-equivalent cyan-forming couplers include the following illustrative couplers: l l-hydroxy-4-acetoxy-Z-naphthamide 2. l-hydroxy-4-acetoxy-N-[a-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide 3. l-hydroxy-4-acetoxy-N-octadecyl-3,5 '-dicarboxy-2- naphthanilide l-hydroxy-4-thiocyano-N-[a-2,4-di-tert-amylphenoxy butyl]-2-naphthamide 5. l-hydroxy-4-(pentafluorophenoxy)-N-{B-{4-[a-(2,4-ditert-amylphenoxy)acetamido1phenyl lethyll-2-naphthamide 6. l-hydroxy-4-(4-nitrophenoxy)-N-[a-2,4-di-tertamylphenoxy)butylI-Z-naphthamide 7. l-hydroxy-4-(4-chlorophenoxy)-2tetradecyloxy-2- naphthanilide The DIR couplers used to advantage in the second light-sensitive layer of my photographic elements are advantageously represented by the formula:

wherein C,, is the residue of any nondiffusible coupler including those represented by the structures attached to, but not including, the Y groups, that is, Y. Y, Y and Y in Formulas H, W, VII and Vlll, respectively, and 2 represents a group which does not contain a chromophore, will not couple with oxidized color developer to produce a dye, is not a development inhibitor while it is attached to C,, but is a group that upon release from C, during color development either is or forms a development inhibitor, and includes such groups as:

l. a monothio group, such as, an alkylmonothio group (usually having from 6 to l0 carbon atoms), an arylmonothio group (generally a phenyl or naphthyl), a cycloalkanemonothio group (generally having 5 to 6 carbon atoms in the ring), a carbon-containing hctcrocyclic monothio group (generally having a 5 to six -membered ring containing at least one heteronitrogcn, oxygen or sulfur atom and preferably 1 to four heteronitrogen atoms) including heterocyclic radicals, such as, tetrazolyls, triazinyls, triazolyls. oxazolyls, oxadiazolyls, diazolyls, thiazyls, thiadiazolyls. benzoxazolyls, benzothiazolyls, pyrimidyls, pyridinyls, quinolinyls, etc and in which the aryl-, cycloalkaneand heterocyclicmoieties of the monothiogroup are either unsubstituted or substituted with groups, such as, nitro, halogen (chlorine, bromine, iodine, fluorine), lower alkyl, lower alkylamido, lower alkoxy, lower alkylsulfonamido. a-chloroacetylthio, lower the couplers may be dispersed in natural resin-type solvents as described in Martinez U.S. Pat. No. 2,284,877; or the couplers may be dissolved in monomeric solution which is then polymerized in the presence of gelatin to produce dispersions of the coupler in the polymer as described in U.S. Pat. No. 2,825,382. Alternately, the color-forming couplers can be of the fattail" variety, that is, the Fischer type which have solubilizing groups on them which render them soluble in alkaline solution.

The selection of the particular coupler(s) and optical sensitizing dye(s) (when needed) for use in my elements will depend upon the particular use for which the material is to be designed. The important thing is that the first light-sensitive layer records only one image and the second light-sensitive layer records only another image and that the latent image in one layer is reproduced as a visible image that is vividly different than the latent image reproduction in the other layer.

In the photographic elements of my invention that use a bleachable light-filtering layer between the two light-sensitive layers to confine the image exposures to the appropriate layers, any of the well-known removable light-absorbing dyes having the desired light-absorbing characteristics may be used. Preferably, these dyes are water-soluble dyes which have acid substituents on them, e.g., sulfo, sulfoalkyl, carboxy, carboxyalkyl, etc. or dyes that have dialkylaminoalkyl substituents on them so the dyes are washed out of the emulsion during photographic processing. Other dyes used to advantage are bleached by the alkaline sulfite in the developer solutions or the thiosulfate ion in the hypo fix bath during the photographic processing. lncluded among light-absorbing dyes used to advantage are the cyanines, rnerocyanines, styryl, cinnamylidene, oxanol dyes, etc., such as those described in U.S. Pat. Nos. 2,298,733; 2,537,472; 2,622,082; 2,691,579; 2,843,486; 2,856,404; 3,247,127; etc. These dyes have no appreciable affect on the sensitivity of the silver halide, that is, they are neither sensitizers or desensitizers so that it is not necessary to use mordants to hold them precisely in the filter layer, however, it may be advantageous to use appropriate mordants, for example, basic mordants, such as are described in Minsk U.S. Pat. No. 2,882,156 for mordanting dyes having acid substituents. Illustrative dyes which are used to advantage in my elements include the following:

Dye No. Dye Name 1 Bis( l n-butyl-3-carboxymethylhexahyclro-2,4,6

trioxo-S-pyrirnidine)pentamethinoxonol 2 Bis( l-carboxymethylhexahydro-3-phenyl-2,4,6-

trioxo-S-pyrimidine)pentamethinoxonol 3 Bis(l-n-butyl-3-carboxymethylhexahydro-2,4,6

trioxo-S-pyrimidine)trimethinoxonol 4 Bis( l-carboxym ethylhexahydro-3-n-octyl-2,4,6-

lrioxod-pyrimidine)methinoxonol S Anbydro-S -chloro-9-ethyl-3-methyl-3 '(3- sulfobutyl)-4,5-bcnzothiacarbocyar|ine hydroxide, monosult'onated 6 Anhydro3,3'-diethyl-9-melhyl-4,5; 4', 5-

dibenzothia-carbocyanine hydroxide, disulfonated 7 Anhydro-9-ethyl-3,3'-dimethyl4,5; 4, 5

dibenzothia'carboeyanine hydroxide, disult'onated 8 Anhydro-3,3,9-triethyl-5,5di(p-sulfophenyl)- oxacarbocyanine hydroxide 9 Anhydro l,1-diethyl-2,2'-cyanine hydroxide, monosulfohated 4-l(3ethyl-2( 3H )-benzoxazlylidene)ethylidenel-Iimethyll -p-sulfophenyl-Z-pyrazolimS-one, rnonosulfonated 4 144 3-ethyl-Z-( 3H'benzoxazolylideney2- butenylidenel-3-methyl-1p-sulfopheny1-2- pyrazolinone, monosull'onated Colloidal silver, such as, Carey-Lea silver dispersed in gelatin is advantageously used in place of blue light-absorbing dyes in my photographic element. This filter material is well known in the art and is removed by the bleaching and fixing steps during photographic processing.

Any of the oxidized color developing agent scavengers known in the prior art may be used to advantage in the lightfiltering layer between the first and second light-sensitive emulsion layers. Particularly efficacious for this purpose are the ballasted hydroquinones such as the higher alkyl-substituted hydroquinones in which the alkyl groups have from 7 to 22 carbon atoms, e.g. dioctyl hydroquinone, didodecyl hydroquinone, dipentadecyl hydroquinone, didocosyl hydroquinone, etc.

My photographic elements are developed with photographic alkaline color developer solutions containing any of the primary aromatic amino color developing agents used in color photography including p-phenylenediamines, such as, 3- acetamido-4-amino-N,N-diethylaniline, p-amino-N-ethyl-N- Bhydroxyethylaniline sulfate, p-aminoethyl-B-hydroxyethylaniline, N,N-diethyl-p-phenylenediamine, Z-amino 5- diethylaminotoluene, N-ethyl-B-methylsulfonamidoethyl-3- methyl-4-arninoaniline, 4-amino-N-ethyl-3-methyl-N-(B'sulfoethy1)aniline and the like. Reference is made to Bent et al. .1.A.C.S., 73, 3100-3125 (1951) for additional typical suitable color developing agents. Benzyl alcohol, ascorbic acid, alkali metal bromide, alkali metal thiocyanate, alkali metal thiosulfate, competing couplers, auxiliary developers and other addenda used in color developing solutions are also used to advantage in my color developers.

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

EXAMPLE 1 A piece of transparent cellulose acetate film support is coated with a coarse-grain blue-sensitive camera speed gelatino silver bromiodide emulsion containing the coupler, l- (2,4,6-trichlorophenyl)-3-pentadecyl-4-chloro-5-pyrazolone. Over this layer is coated a rapid developing fine-grain greensensitized gelatino silver chlorobromide emulsion containing the DIR coupler, 5-methoxy-2'[a-(3-pentadecylphenoxy)butyramido]-4-(l-phenyl-5-tetrazolylthio)-phenol. The gelatino silver halide emulsions used above are made as described by Trivelli and Smith, Photo. Journal, 79, 330 (1939). After drying, this element is exposed to the optically combined registered light images from a SLR radarscope having blue lightemitting phosphors in its screen and a MTI radar scope having green light-emitting phosphors in its screen. The map image from the SLR radarscope is recorded in the first lightsensitive layer and the moving target image is recorded in the second light-sensitive layer. A developing solution having the following composition:

Benzyl alcohol ml. N-hydroxymethyl-Ncthyl-P-aminoalinehydrogen sulfate monohydrate 10.0 g. Sodium carbonate monohydrate 20.0 g. Ascorbic acid 0.35 g. Potassium bromide 0.75 g. Distilled water to 1. liter Sodium hydroxide to pH 11.0

is applied to the top or second light-sensitive layerv Upon penetration of the developing solution, the top layer of the film produces a silver and cyan dye image from the latent image of the MTl and liberates phenyl mercaptotetrazole which accompanies the developer solution in an image-wise pattern into the first light-sensitive layer where a silver and magenta dye image is formed of the SLR latent image excepting under the areas where images are formed in the top second light-sensitive layer where no developed image is formed (in the first light-sensitive layer). The developed photographic material is then immersed in a conventional potassium ferricyanide, potassium bromide bleach solution followed by a conventional sodium thiosulfate hypo fix leaving only bright cyan dye images of the MT! in the top layer and a magentacolored image of the SLR map in the bottom layer. No msgem ta image is formed directly under and slightly outside the cyan dye images even in areas where a latent image was recorded in the first light-sensitive layer. Even very minute MTI cyan color images are very easily discernible in the processed film because of the bright cyan dye enhanced by the clear area surrounding it.

EXAMPLE 2 A material is coated like that described in example 1 excepting that no color-forming coupler is used in the first lightsensitive layer. This material is exposed and color developed as described in example 1, then treated with a stabilizing solution containing thiourea in order to stabilize the unexposed, undeveloped silver halide so that it will not printout on exposure to light. Good readily discernible cyan dye images which are formed in this element are surrounded by the underlying silver image in the first light-sensitive layer. This very rapidly produced image reproduction can be studied and subsequently fixed with sodium thiosulfate fixing bath to remove the unexposed, undeveloped silver halide.

EXAMPLE 3 A photographic material is made like that described in example l excepting that a green-sensitized silver chlorobromoiodide emulsion is used in place of the blue-sensitive silver bromoiodide in the first light-sensitive layer and a blue-sensitive silver chlorobromide emulsion is used instead of the green-sensitized silver chlorobromide in the second lightsensitive layer. This material is exposed using a SLR radarscope having a green light-emitting phosphor and a MTI radarscope having a phosphor emitting blue light. Upon development, as described in example 1, this material produces images comparable to those in example 1.

EXAMPLE 4 A photographic material is made similar to that described in example I excepting that the DIR coupler, l-hydroxy-4-( lphenyl-S-tetrazolylthio)2-tetradecyloxy-Z-naphthanilide is used .in place of 5-methoxy-2-[a-(3-pentadecylphenoxy)-butyramido]-4-( l-phenyl-5-tetrazolylthio)phenol. Similar results are obtained to those as obtained in example 1 from exposure and processing of this material as described in example 1.

EXAMPLE 5 A photographic material is made like that described in example excepting that the coupler, l-hydroxy-4-acetoxy-N-[ a-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide is used in the first light-sensitive layer in place of the coupler, l-(2,4,6- trichlorophenyl)-3-pentadecyl-4-chloro-5-pyrazolone and the DIR coupler, l-phenyl-3-pentadecyl-4-( l-phenyl-S- tetrazolylthio)-5-pyrazolone is used in the second light-sensi tive layer in place of the DIR coupler, 5-methoxy-2-[a-( 3-pentadecylphenoxy )butyramido ]-4-( l-phenyl-S- tetrazolylthio)phenol. Upon exposure and processing as described in example 1, there is produced vividly discernible magenta-colored MTI images surrounded by a narrow, clear area outside of which is a cyan-colored SLR map image reproduction. As in the examples described before, there is no dye image in the first light-sensitive layer underneath the dye images in the second light-sensistive layer of the processed material.

EXAMPLE 6 A clear cellulose acetate film support is coated with a coarse-grain blue-sensitive gelatino silver chlorobromide emulsion containing the coupler, 2-[a-(2,4-di-tertamylphenoxy)butyramido]-4,6-dichloro-5-methylphenol. Over this first light-sensitive layer is coated a gelatin layer containing dioctyl hydroquinone and this layer is in turn coated with a fine-grain rapid developing green-sensitized gelatino silver chlorobromide emulsion containing the DIR coupler, l- 4-(-y -2,4-di-tert-amylphenoxybutyramido)phenyl]-3-ethoxyi6 4-(l-phenyl-5-tetrazolylthio)-5 pyrazolone. Upon exposure and processing as described in example 1, bright, readily discernible magenta-dye images are obtained of the MTI surrounded by narrow, clear images which are in turn surrounded by a cyan-colored SLR map image.

EXAMPLE 7 A photographic material is made similar to that described in example 6 but in which the gelatin layer between the first and second light-sensitive layers contains a colloidal Carey-Lea silver dispersion and a blue-sensitive silver chlorobromide emulsion is used in the second light-sensitive layer instead of the green-sensitized silver chlorobromide emulsion. This material is exposed through the support to the blue light image of the SLR map and through the second light-sensitive layer to a MTI from a blue light-emitting radarscope. The exposing images from the two radarscopes are positioned so that they are in register before the exposure is made. Upon processing, similar good results are obtained to those described in example 6.

EXAMPLE 8 A photographic element is made as described in example I excepting that a red-sensitized fine-grain rapid developing gelatino silver chlorobromide emulsion is used in the second light-sensitive layer in place of the green-sensitized silver chlorobromide emulsion used in example 1. After drying, this material is used as described for example I excepting that the radarscope producing the MTI has a red light-emitting phosphor screen instead of a green light-emitting phosphor screen. Upon development of the exposed material, image reproductions are obtained comparable to those obtained in example 1.

EXAMPLE 9 A photographic element is made similar to that made in ex ample l excepting that a red-sensitive camera speed coarsegrain gelatino silver bromoiodide emulsion is used in place of the blue-sensitive silver bromoiodide emulsion in the first light-sensitive layer and the yellow dye-forming coupler, l1-[4- (hydroxy-phenylsulfonyl)phenoxy]-a-pivalyl-2-chloro-S-[y- (2,4-di-tert-amylphenoxy)butyramido]-acetanilide is used in place of the magenta-forming coupler, l-(2,4,6- trichlorophenyl)-3-pentadecyl-4-chloro-5-pyrazolone. This material is used as described for example 1 excepting that the radarscope used for imaging the SLR map has a red lightemitting phosphor screen. The processed material has bright cyan image reproductions of the MTI surrounded by a yellow dye image reproduction of the SLR map. No yellow dye image is produced directly under the cyan dye images.

EXAMPLE 10 A photographic element is made similar to that made in example l excepting that blueand red-sensitive camera speed gelatino silver bromoiodide emulsion is used in place of the blue-sensitive emulsion coated on the support in example 1. After drying, this element is exposed as described in example 1 except that the SLR radarscope phosphors emit blue light and red light (but no green light). Results similar to those ob tained in example I are obtained when this exposed material is processed as described in example 1. This example shows the: light from two different regions of the actinic spectrum is used advantageously to record one image and light from a third and exclusively different region of the actinic spectrum is used to advantage to record the second image.

Similar results are obtained when still other parts of the actinic spectrum are used including the ultraviolet light, visible light and infrared regions of the spectrum.

described in example 1 excepting that the phosphor used in l the SLR radarscope emits an ultraviolet light image and the phosphor used in the MTl radarscope emits an infrared light image.

Similarly it can be shown that any of the other twoequivalent dye-forming couplers, as well as four-equivalent dye-forming couplers described in this application can be used advantageously in the first light-sensitive layer and that the DIR couplers illustrated in examples 1 through 11, as well as any of the other DlR couplers described in this specification, can be used advantageously in the second light-sensitive layer. Although the examples show the use of gelatin as the hydrophilic colloid material for the layers of my photographic elements, it is understood that any of the other hydrophilic colloids used in photographic layers, especially those mentioned previously, can also be used to advantage. Any appropriate support materials used in photographic elements can advantageously be used in my photographic materials.

EXAMPLE 12 A piece of transparent cellulose acetate film support is coated in succession with (1) a rapidly developing fine-grain green-sensitized gelatino silver chlorobromide emulsion containing the DIR coupler -methoxy-2-[a-(3-pentadecylphenoxy)butyramido]-4-( l-phenyl-S- tetrazolylthio)phenol and (2) a coarse-grain blue-sensitive camera speed gelatino silver bromoiodide emulsion containing the coupler l-(2,4,6-trichlorophenyl)-3-pentadecyl-4- chloro-S-pyrazolone. This material is exposed and processed as described in example 1 giving results that are similar to those in example 1.

EXAMPLE 13 A piece of the photographic material made in example l2 is coated over the outer light-sensitive layer with a third lightsensitive layer comprising a rapidly developing fine-grain redsensitized gelatino silver chlorobromide emulsion containing the DIR coupler a-benzoyl-a-[l-(3-pelargonamidophenyl)-5- tetrazolylthio]acetanilide. The dried material is exposed as described in example 1 excepting that the material is also exposed to a red light image (placed in optical register with the other two light images) emitted by the phosphor of a cathoderay tube which is driven by electronic signals from an infraredsensing element that is scanning the same areabeing covered by the SLR and MT]. Upon processing as described in example l, cyan dye images representing the MTl and yellow dye images representing infrared-radiating objects are vividly discernible against the magenta dye image of the SLR map. No magenta dye image is developed in the photographic material in areas where there is a cyan and/or a yellow dye image.

In addition to the utility illustrated for my photographic elements in the preceding examples, they are used to advantage in other photographic recording systems where it is desired to record a plurality of separate images and be able to study them in superposed relationship especially when one or more of the images is made up of small and especially minute areas, such as, fine lines, small dots, etc. These very fine detailed images are vividly discernible when my photographic materials are used while they would be very difficult to see when reproduced on prior art recording materials, especially in areas where there is an underlying image reproduction.

The invention has been described in detail with particular embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in i the appended claims.

lclaim:

1. A photographic element capable of recording images, said element comprising a support having coated thereon:

l. A first light-sensitive hydrophilic colloid layer comprising a coarse-grain silver halide emulsion sensitive to at least one region of the actinic spectrum of from about 5 my. to about 1,200 mg, and

2. a second light-sensitive hydrophilic colloid layer sensitive to at least one region of said actinic spectrum that is different from the region of said actinic spectrum to which said first light-sensitive layer is sensitive, said second layer comprising a finer grained and more rapidly developing silver halide emulsion than the emulsion in the said first 1 light-sensitive layer, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer, a colorless, nondiffusible development inhibitor-l releasing coupler that reacts with oxidized primary aroi matic amine color developer to form a dye and a diffusi' ble development inhibiting agent, said development in-l hibitor having substantially no development inhibiting effect on the silver halide development in the second light sensitive layer but produces a substantial inhibition of the development of the said silver halide emulsion in the said first light-sensitive layer during color development of said element with a primary aromatic amine color developer; said first light-sensitive layer containing a nondiffusible dyeforming coupler that forms a nondiffusible dye when the dye formed from the said development inhibitor-releasing coupler is diffusible.

2. A photographic camera speed element capable of recording images, said element comprising a support having coated thereon:

l. a first light-sensitive hydrophilic colloid layer comprising a coarse-grain silver halide emulsion sensitive to at least one region of the actinic spectrum of from about 5 my. to about 1,200 my. and a colorless, nondiffusing coupler which reacts with an oxidized primary aromatic amine color developing agent to form a nondiffusible dye, and

2. a second light-sensitive hydrophilic colloid layer sensitive to at least one region of said actinic spectrum that is different from the region of said actinic spectrum to which the said first light-sensitive layer is sensitive, said second layer comprising a finer grained and more rapidly developing silver halide emulsion than the emulsion in the said first light-sensitive layer, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer, a colorless nondiffusible development inhibitor-releasing thioether coupler that reacts with an ox idized primary aromatic amine color developer to form a nondiffusing dye having a different color than the dye formed by the coupler in the said first light-sensitive layer and a diffusible mercaptan development inhibiting agent, i

said inhibitor having substantially no development inhibiting effect on the silver halide development in the said second light-sensitive layer but produces a substantial inhibition of the development of the silver halide in the said first light-sensitive layer during color development of said element with a primary aromatic amine color developer. 3. A photographic element of claim 2 in which the colorless nonidffusible development inhibitor-releasing thioether coupler reacts with an oxidized primary aromatic amine color developing agent to form a nondiffusing dye and a diffusible phenylmercaptotetrazole development inhibiting agent.

4. A photographic element of claim 2 in which the colorless nondiffusible development inhibitor-releasing thioether coupler reacts with an oxidized primary aromatic amine color developing agent to form a nondiffusing dye and a diffusible phenylmercaptotetrazole development inhibiting agent, and in which the said first light-sensitive hydrophilic colloid layer is coated as the first light-sensitive layer on the said support and the said second light-sensitive hydrophilic colloid layer is coated over the said first light-sensitive hydrophilic colloid layer.

5. A photographic element of claim 2 in which the colorless nondiffusible development inhibitor-releasing thioether coupler reacts with an oxidized primary aromatic amine color developing agent to form a nondiffusing dye and a diffusible phenylmercaptotetrazole development inhibiting agent, and in which the said first light-sensitive layer and the said second light-sensitive layer are coated so that the said second lightsensitive layer is nearest the support and between the support and the said first light-sensitive layer.

6. A photographic element of claim 2 in which the support is a transparent support and in which the first light-sensitive hydrophilic colloid layer and the second light-sensitive hydrophilic colloid layers are separated by a hydrophilic colloid layer containing a bleachable blue light-absorber.

7. A photographic element of claim 2 in which the said first light-sensitive layer contains a blue-sensitive silver bromoiodide emulsion and the said second light-sensitive layer contains a green-sensitized silver chlorobromide emul- 8. A photographic element of claim 2 in which the said first light-sensitive layer contains a green-sensitized silver bromoiodide emulsion and the said second light-sensitive layer contains a blue-sensitive silver chlorobromide emulsion.

9. A photographic element of claim 2 in which the said first light-sensitive layer contains a blue-sensitive silver bromoiodide emulsion and the said second light-sensitive layer contains a red-sensitized silver chlorobromide emulsion.

10. A photographic element comprising a support coated in succession on one side with:

l. a first light-sensitive hydrophilic colloid layer comprising a camera speed fine-grain rapidly developing silver chlorobromide emulsion sensitive to a first region of the visible spectrum and contiguous to the said silver chlorobromide emulsion, a first colorless nondiffusible development inhibitor-releasing coupler that forms upon reaction with oxidized primary aromatic amine color developing agent during color development a nondiffusible dye and a diffusible development inhibiting agent which has substantially no effect on the development of the said silver chlorobromide in (l),

. a second light-sensitive hydrophilic colloid layer comprising a camera speed coarse-grain silver bromoiodide coarse-grain sensitive to a second region of the visible spectrum that is different from the said first region to which the said silver chlorobromide emulsion is sensitive and contiguous to silver bromoiodide grains in the said emulsion in (2), a colorless nondiffusible coupler selected from the class consisting of a S-pyrazolone, a phenol, a naphthol and an open-chain coupler that forms upon reaction with oxidized primary aromatic amine, a nondiffusing dye having a color that is different from the color of the dye formed in the said first light-sensitive layer, the

said coarse-grain silver bromoiodide emulsion having a' development induction period such that sufficient I 1 development inhibitor released by development in the said first light-sensitive layer diffuses into the said second light-sensitive layer before any latent image in the said silver bromoiodide emulsion starts to develop and substantially inhibits development of said latent image in areas corresponding to the nondiffusible dye formed in the said first light-sensitive layer, and

3. a third light-sensitive hydrophilic colloid layer comprising a fine-grain rapidly developing silver chlorobromide emulsion sensitive to a third region of the visible spectrum and contiguous to silver chlorobromide grains in the emulsion in this layer, a second colorless nondiffusible development inhibitor releasing coupler that forms upon reaction with oxidized primary aromatic amine colordeveloping agent during color development, a nondiffusible dye having a color that is different from the color of the dyes formed in the said first and said second light-sensitive layers, and a diffusible development inhibiting agent which has substantially no effect on the development of the silver chlorobromide in the said third lightsensitive layer but which substantially inhibits development of any latent image in the said second light-sensitive layer in areas corresponding to the nondiffusible dye formed in the said third light-sensitive layer.

11. A photographic element comprising a support coated in succession with:

l. A first light-sensitive hydrophilic colloid layer comprising a coarse-grain camera speed silver bromoiodide emulsion sensitive to one region of the visible spectrum and contiguous to the said silver bromoiodide emulsion, a colorless nondiffusible coupler selected from the class consisting of a S-pyrazolone, a phenol, a naphthol, and an openchain coupler that forms upon reaction with oxidized primary aromatic amine color-developing agent a nondiffusing dye and 2. a second light-sensitive hydrophilic colloid layer comprising a fine-grain rapidly developing silver chlorobromide emulsion sensitive to a region of the visible spectrum that is different from the region to which the said silver bromoiodide emulsion is sensitive and contiguous to the said silver chlorobromide emulsion, a colorless nondiffusible DIR coupler that forms upon color development a nondiffusible dye having a color that is different from the color of the dye formed in the said first light-sensitive layer and a diffusible development inhibiting agent which has substantially no development inhibiting effect on the said silver chlorobromide emulsion but which produces a substantial inhibition of the development of the said silver bromoiodide emulsion in the said first light-sensitive layer during color development, said DIR coupler having the formula:

wherein Z is selected from the group consisting of a 2- benzotriazolyl group, a 2-naphthotriazolyl group, a Z-aminoarylazoxy group, a 2-amidoarylazoxy group and a monothio radical; and C is a photographic color-forming coupler having substituted in its coupling position, the said Z substituent.

12. A photographic element of claim 11 in which the said DIR coupler has the formula:

wherein Z represents a -SD' group in which D is a heterocyclic radical having 1 to 4 heteronitrogen atoms, said radical being incapable of forming a dye with oxidized aromatic primary amine color-developing agents.

13. A photographic element comprising a support coated in succession with:

l. a first light-sensitive hydrophilic colloid layer comprising a blue-sensitive coarse-grain camera speed gelatin. silver bromoiodide emulsion and the two-equivalent magenta dye-forming coupler, 1-(2,4,6-trichlorophenyl)-3-pentadecyl-4-chloro-S-pyrazolone and 2. a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine-grain rapidly developing gelatino silver bromoiodide emulsion and the cyan dyeforming DIR coupler, 2-a-(3-pentadecylphenoxy)-butyramido]-4-( l-phenyl-5-tetrazolylthio)-5methoxyphenol.

14. A photographic element comprising a support coated in succession with:

l. a first light-sensitive hydrophilic colloid layer comprising a blue-sensitive coarse-grain camera speed gelatin. silver bromoiodide emulsion and the two-equivalent cyan dyeforming coupler, 2-[a-(2,4-di-tert-amylphenoxy)butylamido1-4,6-di-chloro-S-methylphenol and 2. a second light-sensitive hydrophilic colloid layer comprising a green -sensitized fine-grain rapidly developing gelatino silver bromoiodide emulsion and the magenta dye-forming DIR coupler, l-[ 4-(y-2,4-di-tertamylphenoxybutyramido)phenyl]h-3-ethoxy-4-(l-phenyl- 5-tetrazolylthio)-5-pyrazolone.

15. A photographic element comprising a support coated in succession with:

l. a first light-sensitive hydrophilic colloid layer comprising a blue-sensitive coarse-grain camera speed gelatino silver bromoiodide emulsion and the two-equivalent magenta dye-forming coupler, l-(2,4,6-trichlorophenyl)-3-pentadecyl-4-chloro-S-pyrazolone, and

2. a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine-grain rapidly developing gelatino silver bromoiodide emulsion and the cyan dyeforming DIR coupler, l-hydroxy-4-( l-phenyl-S- tetrazolylthio)-2'-tetradecyloxy-2-naphthanilide.

16. A photographic element comprising a support coated in succession with:

l. a first light-sensitive hydrophilic colloid layer comprising a blue-sensitive coarse-grain camera speed gelationo silver bromoiodide emulsion and the two-equivalent cyan dye-forming coupler, 2-[a-(2,4-di-tert-amylphenoxy)butylarnido]-4,6-dichloro-5metholphenol,

. a gelatin layer containing dioctyl hydroquinone and a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine-grain rapidly developing gelation silver bromoiodide emulsion and the magenta dyeforming DIR coupler, l-[4-(a-2,4-di-tert-amylphenoxybutyramido)phenyl]-3-ethoxy-4-( l-phenyl5- tetrazolythio)-5-pyrazolone.

17, A photographic element comprising a support coated in succession with:

l. a first light-sensitive hydrophilic colloid layer comprising a blue-sensitive coarse-grain camera speed gelatino silver bromoiodide emulsion and the two-equivalent cyan dyeforming coupler, l-hydroxy-4-acetoxy-N-[a-(2,4-di-tertamylphenoxy)butyl]-2-naphthamide, and

2. a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine-grain rapid developing gelatino silver bromoiodide emulsion and the magenta dye-forming DIR coupler, l-phenyl-3-pentadecyl-4-( l-phenyl-5- tetrazolylthio)-5-pyrazolone.

18. A process for color developing substantially all of a second latent image in a second light-sensitive silver halide emulsion layer of a photographic element and developing only those parts of a first latent image in a first light-sensitive silver halide emulsion layer of the said photographic element that are not superposed by the visible image reproduction of the said second latent image in which the said element comprises a support coated with: (a) the said first light-sensitive hydrophilic colloid layercontaining a coarse-grain camera speed silver halide emulsion and (b) the said second light-sensitive hydrophilic colloid layer comprising a fine-grain rapidly developing silver halide emulsion and a nondiffusing DIR cou pler that forms upon color development a nondiffusing dye in the said second light-sensitive layer and releases a diffusible development inhibitor, said process comprising the step of contacting the said photographic element with an aqueous alkaline color developer solution so that the latent image in the said second light-sensitive layer is rapidly converted into a silver and dye image and releases a corresponding image-wise pattern of development inhibitor, the said inhibitor having substantially no effect on image formation in the said second light-sensitive layer, and allowing the unused color developer solution containing the said image-wise pattern of development inhibitor to diffuse from the said second light-sensitive layer into and through the said'first light-sensitive layer causing development of the said first latent image therein to a visible image only in areas outside the said image-wise pattern of development inhibitor and producing no visible image from any latent image in the said first light-sensitive layer between the said dye and silver image In the said second light-sensitive layer and the said support.

19. A process for recording two separate, differently colored light images as two different latent images, a first latent image in a first light-sensitive layer and a second latent image in a second light-sensitive layer in a photographic element and reproducing all of the said second latent image as a visible image and those parts of the said first latent image that are not superposed by the visible image reproduction of the said second latent image, the said process comprising the steps of:

l. exposing to the said two light images a photographic element comprising a support coated with: (a) a first lightsensitive hydrophilic colloid layer comprising a coarse grain camera speed silver bromoiodide emulsion responsive to only one of the said light images and (b) a second light-sensitive hydrophilic colloid layer comprising a f inegrain rapidly developing silver chlorobromide emulsion responsive only to the other of said light images and contiguous to the said silver chlorobrornide emulsion a nondiffusible DIR coupler that forms upon color development a nondiffusible dye and a diffusible development inhibiting agent which has substantially no development inhibiting effect on the said silver chiorobromide emulsion but which inhibits development of the said silver bromoiodide emulsion in the said first light-sensitive layer during color development,

2. contacting the said photographic element with an aqueous alkaline solution containing a primary aromatic amine color developing agent to develop a silver and dye image of the said second latent image in the second lightsensitive layer and to subsequently produce a differently colored dye image and a silver image of those areas of the said first latent image in the first light-sensitive layer which do not correspond to the said dye and silver image in the said second light-sensitive layer and producing substantially no visible image reproduction of any latent image in the first light-sensitive layer corresponding to the said dye and silver image in the said second light-sensitive layer.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 62 7 u5 Dated- N ovember l5,*1971 Inventor) Merrill W. Seymour It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shovm below:

Column 1, line 55, replace picture" with --pict1dr)e(s- H Column 6, line 50, replace the formula with RC-CHOC- Column 7, line 16, after 4-sulfophenoxyl-" insert a parentheses line 56, replace "2cyanoacetylcourmarone with -2cyanoacetylcourmarone-.

Column8, lines 7 9 and 17, replace "benzamidoih" with --benzamido/-; lines 22 and 25, replace "equivolent" with -equivalent-.

Column 10, line 26, replace imide" with -imido.

Column ll, line 20, replace :6 methoxy" with --6-methoxy--;

line 26, after "Ll,2d: %,5" delete the parentheses line 32, after "(p-tolyl" delete "O" and insert a parentheses line 35, after "0C (first occurrence) insert a hyphen line 33, after "benzoyl" delete "5! and insert a hyphen line 55, replace ll-phenyl" with 4(l-phenyl--;

line 56 after "1- i l[ replace with C Page 1 of 3 pages.

po-wso Patent No.

UNITED STATES PATENT OFFICE Dated November 16 1971 Inventor(s) Merrill W. Seymour It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column Column Column Column Column Page 2 line line line line line line 42,

13, line 55,

line 67,

1 5, line 52,

line line line line line of 3 pages after "LIZ insert a hyphen after "l-flI insert a hyphen l, after "phefiyl" delete the parentheses replace "tetrazolythio" with --tetrazolylthio)-; after "benzotriazolyl" insert a parentheses replace "tetrazolythio with --tetrazolylthio--;

after "butyl" delete 17".

Dye No. 5, after "methyl-3' insert a hyphen Dye No. 11, after "(311" insert a parentheses replace "hydrozymethyl" with -hydroxyethyl.

replace "gelatin." with --g;elatino--; after "DIR", delete "I";

after "2-" insert a bracket replace "gelatin." with --g;elati no--.

after "phenyl7" delete "h";

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION patent 3,620,7 5 Dated November 16 .1971

Inventor) Merrill W. Seymour It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 21, line 22, replace "gelationo" with -gelatino--;

lines 28 and 29, after "developing" and before "silver" delete "gelation" and insert gelatino.

Signed and sealed this 27th day of June 1 972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents Page 3 of 3 pages.

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3770436 *Dec 23, 1971Nov 6, 1973Konishiroku Photo IndProcess for forming cyan image in light-sensitive color photographic material
US3772002 *Oct 14, 1971Nov 13, 1973Minnesota Mining & MfgPhenolic couplers
US3779763 *Feb 3, 1972Dec 18, 1973Eastman Kodak CoPhenol color couplers
US3932185 *Aug 12, 1974Jan 13, 1976Konishiroku Photo Industry Co., Inc.Multi-layer photosensitive material for color photography
US3960558 *Apr 29, 1974Jun 1, 1976Polaroid CorporationDye free, spectrally sensitive silver halide layers in diffusion transfer films
US3961959 *Jan 28, 1974Jun 8, 1976Konishiroku Photo Industry Co., Ltd.Process for developing a light-sensitive silver halide photographic material
US3990899 *May 6, 1974Nov 9, 1976Fuji Photo Film Co., Ltd.Multi-layered color photographic light-sensitive material
US4003744 *Aug 2, 1974Jan 18, 1977Polaroid CorporationPhotographic products with photosensitive layers of same spectral sensitivity and different speed
US4015988 *Mar 4, 1975Apr 5, 1977Fuji Photo Film Co., Ltd.Multilayer color photographic light-sensitive material
US4029508 *Aug 14, 1975Jun 14, 1977Fuji Photo Film Co., Ltd.Silver halide material containing a yellow color-forming coupler
US4171223 *Jun 23, 1978Oct 16, 1979Agfa-Gevaert, A.G.Light-sensitive color photographic material
US4186012 *Mar 2, 1978Jan 29, 1980Agfa-Gevaert AktiengesellschaftLight sensitive color photographic material containing development inhibitor releasing coupler
US4273861 *Feb 23, 1976Jun 16, 1981Fuji Photo Film Co., Ltd.Multilayer color photographic materials utilizing an interlayer correction coupler
US4855220 *Jan 14, 1988Aug 8, 1989Eastman Kodak CompanyPhotographic element having layer for increasing image sharpness comprising a non-diffusible DIR compound
Classifications
U.S. Classification430/364, 430/505, 430/382, 430/383
International ClassificationG03C7/30, G03C1/46
Cooperative ClassificationG03C7/3029, G03C5/164, G03C7/30541, G03C2007/3034, G03C7/3003, G03C1/46
European ClassificationG03C7/30C, G03C7/30M, G03C1/46