Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
  • G03C2007/3034—Unit layer
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group

Definitions

• 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 nondiffusing color-forming coupler that forms a dye upon color development and (2) a second light-sensitive layer containing a silver halide emulsion preferably a finer grain rapidly developing silver halide and a nondiffusing coupler that forms a dye, and a nondiffusible development inhibitor-releasing hydroquinone compound that releases 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 produce a visible image reproduction of the first light image in the first layer, said visible image reproduction having reduced contrast in areas that correspond to the image reproduction formed in the said second layer.
• This invention is related to photography including sensitive photographic materials and processes for recording a plurality of separate images and reproducing them as vividly different image reproductions.
• red-sensitized silver halide emulsion layer contains a phenolic or naphtholic dye-forming coupler
• green-sensitized silver halide emulsion layer contains a magenta-forming pyrazolone coupler
• blue-sensitive silver halide emulsion layer contains an open-chain yellow dye-forming coupler.
• 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 phosphor-coated radar screen showing moving target information (referred to hereinafter as MTI) from the same area represented or shown by the map.
• SLR side-looking radar
• MTI moving target information
• the radar signals received by the radar scope providing MTI are electronically filtered so that the radar scope shows only images of moving objects.
• 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.
• Another object of my invention is to provide a novel multilayer light-sensitive photographic material and process for recording and reproducting images of at least two colors so that the color development of one image in one layer reduces the contrast of an image in a second layer and at the same time increases the sharpness of the edges of the images.
• one embodiment 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 So to about l,200p.
• a colorforming coupler preferably a nondiffusing coupler
• a second light-sensitive hydrophilic colloid layer containing a silver halide emulsion (preferably 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 lightsensitive layer is sensitive and contiguous to silver halide grains of the emulsion in thesecond light-sensitive layer
• a coupler that reacts with oxidized primary aromatic amine color developer to form a dye image which advantageously has a different color than a dye image formed in the first lightsensitive layer and a nondiffusing development inhibitorreleasing (DIR) hydroquinone compound that cross-oxidizes with an oxidized primary aromatic amine color-developing agent to release
• DIR nondiffusing development inhibitorreleasing
• the finer grained rapidly developing silver halide emulsion is substantially completely developed and the imagewise 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.
• 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.
• 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 of an SLR map which is optically combined and registered with the radar information showing MTI so that the film is exposed in a single step with the SLR map image recorded in the first lightsensitive layer and the radar information showing MTI recorded in the second light-sensitive layer.
• 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.
• a hydrophilic colloid layer containing a bleachable light-absorbing filter that will absorb the exposing image light.
• the two emulsions need not be spectrally sensitized or they can be advantageously spectrally sensitized in any way desired including identical spectral sensitization.
• 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 coupler that reacts with oxidized primary aromatic amine color-developing agent to form a first nondiffusible dye and contiguous to this same emulsion a DIR hydroquinone compound that cross-oxidizes with an oxidized primary aromatic amine color-developing agent and then releases 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 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
• 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 diffuses 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.
• 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 v that is different from those to which the others respond.
• the couplers are advantageously chosen so that they produce upon color development differently colored dyes.
• dyes are chosen which are as different as possible, however, when more than three or four 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.
• 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 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.
• a non-light-sensitive hydrophilic colloid layer containing a scavenger to prevent oxidized colordeveloping agent from wandering from one light-sensitive layer to the next.
• My 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 imagewise pattern corresponding to the silver and dye image formed.
• the imagewise pattern of developmentinhibiting agent and 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 colordeveloping 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.
• 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.
• 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.
• 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.
• couplers forming diffusible dyes are advantageously used in the light-sensitive layers or packets, or alternatively mixtures of couplers that form nondiffusible dyes together with couplers that form diffusible dyes are advantageously used in one or all of the lightsensitive layers or packets.
• the couplers in such a mixture can form dyes that have the same or different spectral absorptions providing differently colored nondiffusible dyes are formed'in the different light-sensitive layers or packets and differently colored diffusible dyes are formed in the different light-sensitive layers or packets.
• the diffusible dye images are transferred to a separate mordanted reception sheet by contacting during development or a reception sheet that is an integral part of the element with a strippable layer coated between one of the image-forming layers and the mordant layer of the reception sheet. After development, the reception sheet is separated from the image-forming layers carrying the composite of the diffusible dye images. It is advantageous to remove residual developer solution from the image-bearing reception sheet. Where nondiffusible dye images are formed in the image-forming layers, these are washed, then fixed, or bleached and fixed, or blixed, then washed as described previously.
• my DlR hydroquinone compounds are incorporated advantageously in one or more layers of multilayer materials for color photography having differently sensitized silver halide emulsions each incorporating an appropriate nondiffusing dye-forming coupler that forms a nondiffusible dye image that is complementary in color to the colbr of light the emulsion is sensitive to or sensitized to.
• a typical material has a support coated with a red-sensitive silver halide emulsion with incorporated cyan dye-forming coupler, a green-sensitive silver halide emulsion with incorporated magenta dye-forming coupler and a blue-sensitive silver halide emulsion with incorporated yellow dye-forming coupler with one or more of my DIR hydroquinone compounds incorporated in one or more of the light-sensitive layers.
• the layers are advantageously coated in the order mentioned or in various other orders.
• the DIR hydroquinone compound is advantageously incorporated as an alkali metal salt, or in any of the well-known coupler solvents used in the art.
• the compound When incorporated in a coupler solvent, the compound is incorporated along with the coupler in the same dispersion or in a separate coupler solvent dispersion or the compound is distributed between the coupler dispersion and separate dispersion.
• My DlR hydroquinone compounds are usually used in a light-sensitive layer where it is desired to have the image development in that layer (during color development) form an imagewise pattern of development inhibitor that diffuses into the adjacent 1ayer(s) and inhibits the color development of the latent images according to the mentioned imagewise pattern.
• This interimage effect is valuable for various purposes including masking unwanted light absorption in one or more of the image dyes. In addition to this effect, there is a valuable increase in sharpness at the edge of the dye images.
• My DIR hydroquinone compounds are particularly advantageously used because the same compound can be used not only in each image-forming layer but in interlayers as well, if desired, to produce a uniform increase in sharpness of each of the dye images, since these compounds are not only colorless but do not form dyes. Where different degrees of the interimage effect or the edge effect are desired different DlR hydroquinone compounds are used.
• any of the usual supports used in photographic materials can be used to advantage in making mu 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.
• hydrophilic colloids used in the preparation of photographic elements are used to advantage in preparing the layers of my photographic materials.
• Illustrative 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 18 advantageously a finer grained rapidly developing silver halide emulsion, e.g., silver chlorobromide, silver chlorobromoiodide, etc., and is preferably of camera speed.
• the same silver halide emulsion is advantageously used in each of the three layers of an element designed for color photography providing they are given appropriate spectral sensitization for the particular layer they are to be used in.
• 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; Brooker et al. U.S. Pat. No. 2,493,748, issued Jan. 10, 1950; Sprague U.S. Pat. Nos.
• the photographic silver halide emulsions and other layers on my photographic elements can contain any of the addenda generally utilized in photographic elements including speedincreasing materials, antifoggants, coating aids, gelatin hardeners, plasticizers, ultraviolet absorbers and the like.
• the DlR development inhibitor-releasing hydroquinone compounds used in my photographic elements release development-inhibiting mercaptans that are diffusible in the layers of my photographic materials. 1t is believed that the DlR hydroquinone compound cross-oxidizes with the oxidation product of primary aromatic amine color-developing agents. As a result of this cross-oxidizing reaction. the hydroquinone is oxidized to the corresponding quinone. It is from this quinone only that the diffusible development-inhibiting mercaptan is split and released.
• the DlR compounds of my invention are nondiffusible. or ballasted, heterocyclic thio-substituted hydroquinoncs which react with oxidized color-developing agent to form a diffusible mercaptan development inhibitor.
• the heterocyclic radical of the heterocyclic thio substituents are carbon-containing radicals generally having from four to six atoms in the ring with at least one heteronitrogen, oxygen, sulfur, or selenium atom and preferably from one to four heteronitrogen atoms.
• thio-substituted hydroquinone compounds of this invention can be masked with an alkaline-splittable group, that is, one or both of the hydroxyl groups of the hydroquinone can be replaced with any suitable substituent, such as, an acyl group which splits off under alkaline conditions to regenerate the hydroxyl group.
• a masking group inactivates a hydroxyl group of the hydroquinone compound. Masked hydroquinone com pounds can be incorporated directly in light-sensitive silver halide systems.
• the DlR hydroquinone compounds used advantageously in my invention include the compounds having the formula:
• S- is a monothio radical which is split from the DIR compound when the said compound cross-oxidizes with oxidized color developer
• Rad represents a wide variety of photographically inert carbon-containing heterocyclic radicals that are diffusible in the layers of my photographic materials and form mercaptan with the monothio connecting or linking radical when the connecting radical is split from the quinone of the DIR hydroquinone compound
• these heterocyclic radicals generally contain at least one heteronitrogen, oxygen, sulfur, or selenium and preferably one to four heteronitrogen atoms with no hydrogen atom attached to nitrogen atom(s).
• the photographically inert Rad radical of the formula includes heterocyclic radicals, such as, a l-phenyltetrazolyl, (e.g., l- (alkylphenyl)tetrazolyl in which the alkyl group has from one to four carbon atoms, a l-(alkoxyphenyl)tetrazolyl in which the alkyl moiety has from one to four carbon atoms, a l- (halophenyl)tetrazolyl in which the halogen is chlorine, bromine, fluorine, iodine, etc., a l-(nitrophenyl)tetrazolyl), an oxazolyl (e.g., 4-methyloxazolyl, S-methoxyoxazolyl, etc.), a benzoxazolyl (e.g., benzoxazolyl, S-methylbenzoxazolyl, 5- chlorobenzoxazolyl, 6-ethoxy
• an imidazole e.g., benzimidazole, o-chlorobenzimidazole, S-methpxybenzimidazole, S-methoxybenzimidazole, etc.
• a pyrimidyl e.g., a pyridinyl (e.g., pyridinyl, 3-methylpyridinyl, 4chloropyridinyl, S-ethoxypyridinyl, etc.).
• a quinolinyl e.g., quinolinyl, 4- chloroquinolinyl, S-methoxyquinolinyl, etc.
• the Ball in the above formula is a ballast group that's a photographically inert, organic radical of such molecular size and configuration as to render DIR hydroquinone compouhds nondiffusing in my photographic materials in the alkaline color development solution, and 0, represents the hydrogen atom, the SO M group, the COOM group; M represents a hydrogen atom or an alkali metal atom, e.g., sodium, potassium, lithium, etc.; Q and 0 each represent the same or different member such as hydrogen, alkyl having from one to carbon atoms (e.g., methyl, ethyl, octyl, decyl, etc.).
• DIR hydroquinone compounds used to illustrate are as follows:
• any of the conventional four-equivalent or two-equivalent nondiffusing couplers used in photographic elements are used to advantage in the light-sensitive layers of my photographic materials, however, it is preferred to use the two-equivalent couplers.
• DIR development inhibitor releasing
• 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 openchain 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 acylacetamidc couplers include the alkoylacetamide couplers, the aroylacetamide couplers, the pivalylacetamide couplers, etc.
• RJI JCII X ballasting groups are very well known in the artv Whendesired, the ballasting groups are provided with solubilizing groups.
• Typical four'equivalent yellow-forming couplers include the following:
• the two-equivalent yellow forming couplers are derived from the types of parent four-equivalent couplers by replacing one of the two hydrogens on the aplha-carhon (LC methylene) with any nonchromophoric coupling off group m eluding groups such as the fluorine atom. the chlorine atom, an acyloxy group, a cyclooxv group and a thlocyano group
• Typical two-equivalent couplers used to advantage included the alpha-fluoro couplers of U.S. Pat. No. 3,277,155, the achloro couplers of U.S. Pat. No.
• the two-equivalent open-chain yellow-forming couplers include those represented by the formula:
• Y is a coupling off group, such as, the chlorine atom, the fluorine atom, the thiocyano group, an acyloxy group [e.g., 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 aryloxoy 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, a alkthio group and an acyloxy group [e.g.
• Typical illustrative examples of two-equivalent yellowforming couplers include the following:
• a-pivalyl-a-stearoyloxy-4-sulfamylacetanilide 8.
• a-pivalyl-aa-( 3 -pentadecylph enoxy )acetoxy 1- 3 5 stituted S-pyrazolone couplers that are incorporated in photographic emulsion layers are used to advantage.
• the 4-equivalent magenta-forming couplers used according to my invention includes those having the formula:
• R is as described previously and R represents a group such as an alkyl group, a substituted carbamyl 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.
• 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 4-equivalent magenta-forming couplers include the following:
• the two-equivalent couplers are derived from the four equivalent parent couplers by replacing one of the hydrogens on the carbon in the 4-position of the pyrazolonc ring with a nonchromophoric coupling off group.
• Examples of coupling off groups used to advantage in two-equivalent magenta-forming couplers are the thiocyano group illustrated by the couplers in Loria U.S. Pat.
• the two-equivalent magenta-forming couplers used according to my invention include those having the formula:
• N ?R' R-N I C-JIH-Y' 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, and alkoxy group, the chlorine atom, the fluorine atom, the sulfo group, etc.
• Typical illustrative examples of two-equivalent magentaforming couplers include the following: j
• the four-equivalent cyan-forming couplers used according to my invention include those having the formulas:
• 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 aklylsulfamyl group, an arylsulfamyl group, a heterocyclic sulfamyl group, etc.), a substituted carbamyl group (e.g., an alkylcarbamyl group, an arylcarba
• Typical four-equivalent cyan-forming couplers include the 7 following illustrative examples:
• Coupled among the coupling off groups are the acyloxy group illustrated by the 4-acyloxyphenols and 4 acyloxynaphthols of Loria U.S. Pat. No. 3,3ll,476, issued Mar. 28, 1967, the cyclooxy group illustrated by the 4- cyclooxy naphthols of Loria U.S. Pat. application Ser. No. 483,807, filed Aug. 30, I965, the thiocyano group illustrated by the 4-thiophenols and 4-thionaphthols of Loria U.S. Pat. No.
• the two-equivalent cyan-forming couplers used according to my invention include those having the formulas:
• the colored color-forming couplers used according to my invention are represented by formulas 111, V V111 and IX in which the Y, Y', Y and Y groups respectively are not as defined previously but are groups which contain a chromaphore such as an arylor heterocyclic azo group. Representative colored color-forming couplers are described by patents such as Vittum et al. U.S. Pat. No.
• the DIR couplers used to advantage in my photographic elements include those described by such U.S. Pat. Nos. as 3,148,062; 3,227,554, etc.
• ballasted DlR hydroquinone compounds and couplers used in my invention are advantageously dispersed in highboiling, crystalloidal compounds which can be used as a vehicle for incorporating the compounds and coupler in the photographic cmulsion according to methods well known in the art.
• Various other known methods of incorporating the DIR hydroquinone compounds and color forming couplers in our element are also utilized.
• the low solvent dispersions described in Fierke U.S. Pat. No. 2,801,107 are used to advantage; or the compounds and couplers are dispersed in natural resin-type solvents as described in Martinez U.S. Pat. No.
• the compounds and couplers are 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.
• the MR hydroquinone compounds and/or color-forming couplers can be of the "fat-tail” variety, that is, the Fischer type which have solubilizing groups on them which render them soluble in alkaline solution.
• nondiffusing used herein as applied to the DIR hydroquinone compounds has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through organic colloid layers. such as gelatin. comprising the sensitive elements of the invention.
• diffusible as applied to the mercaptan development inhibitors released from the DlR compounds denotes materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of the nondiffusing" materials from which they are derived in alkaline colordeveloping solutions.
• the selection of the particular DIR hydroquinone compound(s), 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 he 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
• the DlR hydroquinone compounds of my invention are advantageously used over a wide range 01 coating rates usually about 2 mg./ft. or more, and preferably in the range from about 5 mgJlt. to about 100 mg./ft 2
• the optimum coating rate will depend upon the particular emulsions used and the results desired. The optimum rates are easily determined by methods well known in the art.
• any of the well-known removable light-absorbing dyes having the desired light-absorbing characteristics may be used.
• 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.
• 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.
• Included among light-absorbing dyes used to advantage are the cyanines, merocyanines, 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.
• trioxu-Spyrimidinc)pentamethinoxonol 2 Bis( l-carboxymethylhexahydro-Il-phcnyl 2,4,6
• dibenzothiacarbocyaninc hydroxide disulfonatcd 7 Anhydro -cthyl-3,3'-dimcthyl-4,5; 4 5
• dibcnzothiacarhocyanine hydroxide, disull'onatcd 8 Anhydro-3,3', 9-tricthyl5,5'-di(p-sull'ophcnyl) oxacarbocyanine hydroxide 9 Anhydro-l ,l '-dicthyl- 2,2'-cyaninc hydroxide,
• munosulfonatcd 4-
• 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 light filtering layer between the first and second light-sensitive emulsion layers.
• Particularly efficacious for this purpose are the ballasted hydroquinones such as'the higher alkyl sub stituted hydroquinones in which the alkyl groups have from seven to 22 carbon atoms. e.g., dioctyl hydroquinone, didodecyl hydroquinone, dipentadecyl hydroquinone, didocosyl hydroquinone.
• DlR hydroquinone compounds of my invention are also used advantageously in inter layers to obtain a development-inhibiting affect in addition to the above-mentioned scavenging effect
• 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- B-hydroxyethylaniline sulfate.
• Benzyl alcohol, ascorbic acid, alkali metal bromide, alkali metal thiocyanate, alkali metal thiosulfate, competing coupler, auxiliary developers and other addenda used in color-developing solutions are also used to advantage in my color developers.
• EXAMPLE I A piece of transparent cellulose acetate film support is coated with a coarse grain blue-sensitive camera speed gelatino silver bromoiodide 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 green-sensitized gelatino silver chlorobromide emulsion containing the cyan dye-forming coupler, 2-[a(3-pentadecylphenoxy )butyramido]-5-methoxy-phenol and the DIR hydroquinone compound No.
• 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 imagewise 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 EXAMPLE 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 magenta 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 MTl 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 I, then treated with a stabilizing solution containing thiourea in order to stabilize the unexposed. undeveloped silver halide so that it will not print out 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 sub sequently 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-senstive layer and a lchlorobromide emulsion is used instead of the green-sensitized silver chlorobromide in the second light-sensitive layer.
• This material is exposed using an SLR radar scope having a green-light-emitting phosphor and an MTl radar scope having a phosphor emitting blue light. Upon development, as described in example 1, this material produces images comparable to those in example I.
• EXAMPLE 4 A photographic material is made similar to that described in example 1 excepting that the DIR hydroquinone compound No. 8, i.e., 2,S-dimethyl-3-pentadecyl-6-(2 benzothiazolylthio)-hydroquinone, is used in place of DIR hydroquinone compound No. 9. Similar results are obtained to those as obtained in example I from exposure and processing of this material as described in example 1.
• DIR hydroquinone compound No. 8 i.e., 2,S-dimethyl-3-pentadecyl-6-(2 benzothiazolylthio)-hydroquinone
• EXAMPLE 5 A photographic material is made like that described in example l excepting that the coupler, l-hydroxy-4-acetoxy-N-l a-(2,4-di-tert-amylphenoxy)butyll-2-naphthamide is used in the first light-sensitive layer in place of the coupler, l-(2,4,6- trichlorophenyl l-3-pentadecyl-4-chloro-5-pyrazolone and the DIR hydroquinone compound No.
• EXAMPLE 6 A clear cellulose acetate film support is coated with a coarse grain blue-sensitive gclatino silver chlorobromide emulsion containing the coupler, 2-[a-(2,4-di-tertamylphenoxy )-butyramido I-4,6-dichloro-S-methylphenol.
• a gelatin layer containing dioctyl hydroquinone 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 rapidly developing green-sensitized gclatino silver chlorobromide emulsion containing the magenta dycforming coupler, l-l 4-( 2,4-di-tert-amylphenoxybutyramido)phenyll-3-cthoxy-5pyrazolone, and the development inhibitor releasing hydroquinone compound No.
• EXAMPLE 8 A cellulose acetate film support is coated in succession on one side with (l) a layer containing a coarse grain green-sensitized gelatino silver chlorobromide emulsion, and the nondiffusible magenta dye-forming coupler, l-phenyl-3- ⁇ 3-[d-(3- pentadecylphenoxy)-acetamido]benzamido ⁇ -5-pyrazolone dispersed in dibutylphthalate, (2) a gelatin layer containing 2- octadecyl-S-sulfohydroquinone potassium salt and (3) a layer containing a fine grain rapidly developing red-sensitized gelatino silver chlorobromide emulsion, DIR hydroquinone compound No.
• l i.e., 2- ⁇ 4-[3-(4-t-amyl-x-sulfophenoxy)benzamido]-phenethyl ⁇ -x-( l-phenyl-S- tetrazolylthio)hydroquinone sodium salt and cyan dye-forming coupler.
• One piece of the coated material described is coated on the support side away from the light-sensitive layers, with a removable antihalajtion backing.
• EXAMPLE 9 l l A photographic element is made similar to that made in example l excepting that a red-sensitive camera speed coarse grain gelatino silver bromoidide emulsion is used in place of the blue-sensitive silver bromoiodide emulsion in the first light-sensitive layer and the yellow dye-forming coupler, a[4- (hydroxy-phenylsulfonyl)phenoxyl-a-pivalyl Z-chIoro-S-[ (2,4-di-tert-amylphenoxy)butyramido]acctan
• EXAMPLE 10 A photographic element is made similar to that made in example 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 I. After drying, this element is exposed as described in example I except that the SLR radar scope phosphors emit blue light and red light (but no green light). Results similar to those obtained in example 1 are obtained when this exposed material is processed as described in example I. This example shows that 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.
• EXAMPLE 11 A photographic element is made similar to that made in example excepting that an ultraviolet-sensitive camera speed gelatino silver bromoiodide emulsion is used in place of the blue-sensitive emulsion coated on the support and an infraredsensitized gelatino silver chlorobromide emulsion is coated over it instead of the green-sensitized emulsion used in example 1. After drying, this material is exposed and processed as described in example I excepting that the phosphor used in the SLR radar scope emits an ultraviolet light image and the phosphor used in the MT] radar scope emits an infrared light Image.
• 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 DlR hydroquinone compounds illustrated in examples I through 2. as well as any of the other DlR hydroquinone com pounds described in this specification, can be used advantageously in the second light-sensitive layer.
• 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 l) a rapidly developing fine grain green-sensitized gelatino silver chlorobromide emulsion containing the DlR hydroquinone compound No 6, Le, 2-[4- (3,S-disulfobenzamido)phenethyll x-(2-benzoxazolylthio)hydroquinone disodium salt dihydrate, and 2-la (3-pentadecylphenoxy)butyramidol-5-methoxyphenol 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-5-pyrazolone. This material is exposed and processed as described in example l giving results that are similar to those in example I.
• EXAMPLF 13 A piece of the photographic material made in example 12 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 DlR hydroquinone compound No. 6 and yellow coupler. aacetoxy-a- ⁇ EH- (2,4-di-t-amylphen0xy )butyramidolbenzoyll 2-methoxyacetanilide.
• the dried material is exposed as described in example I 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 infrared sensing element that is scanning the same area being covered by the SLR and MT].
• cyan dye images representing the MTI 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.
• EXAMPLE 14 Film A is made by coating in succession on one side of a cel lulose acetate film support (I) a red-sensitized gelatino silver bromoiodide emulsion layer containing DIR hydroquinone compound No.
• Control Film B is made like Film A but contains no DIR hydroquinone compound. Films A and B are given red light exposures under a step tablet and each uniformly flashed to green light then color processed using the Processing Steps for Eastman Color Negative Film, Type 5248" described by Hanson and Kisner in Society of Motion Picture and Television Engineers, 61, pages 667-70I. Dec, I953 A comparison of the developed films shows that the development of the magenta dye image in Film A is decreased in proportion to the exposure and development in the underlying cyan layer and thus in proportion to the amount of development inhibitor released from compound No. 1. Improved image sharpness is particularly evident.
• EXAMPLE Films C and D are made like Films A and B (control) respectively in example 14 excepting that yellow-colored magenta dye-forming coupler, I-(2,4,6-trichlorophenyl)-3-l 3[a-(2,4-di-t-amylphenoxy )acetamido1benzamido l-4-(4- methoxyphenylazo)-5-pyrazolone is used in (3), the outer layer, in addition to the main magenta image-forming coupler, and red-colored cyan dye-forming coupler.
• yellow-colored magenta dye-forming coupler I-(2,4,6-trichlorophenyl)-3-l 3[a-(2,4-di-t-amylphenoxy )acetamido1benzamido l-4-(4- methoxyphenylazo)-5-pyrazolone is used in (3), the outer layer, in addition to the main magenta image-forming coupler, and red-colored cyan
• Films E and F are made like Films C and D respectively excepting that DIR coupler, l-hydroxy-N-[8-2,4- di-t-amylphenoxy)butyl ]-4-( l-phenyI-5-tetrazolylthio)-2- naphthamide is added to (l) and DIR coupler, l- ⁇ 4-[a-(3- pentadecylphenoxy)butyramido1phenyl ⁇ -3-ethoxy-4-( lphenyl-S-tetrazolylthio)-5-pyrazolone is added to layer (3
• Film E shows not only the effect demonstrated by the DIR hydroquinone compound in Film A but also additional color correction provided by the presence of the colored colorforming couplers and the DIR couplers.
• the DIR hydroquinone compounds of my invention can be used in color photographic coatings in combination with other DIR hydroquinone compounds of my invention as well as with diffusible or nondiffusible, colorless or colored, couplers which form nondiffusible or diffusible image dyes or leuco dyes, or any combination of such couplers.
• My DIR hydroquinone compounds also can be used in combination with diffusible or nondiffusible DIR couplers such as those described in US Pat. Nos. 3,227,554 and 3,148,062, either alone or in combination with any of the above-mentioned couplers.
• My DIR hydroquinone compounds are also advantageously incorporated in photographic coatings together with developer compounds such as, for example, hydroquinones, p-phenylenediamines, l-phenyl-3-pyrazolidones, as well as developing agent precursors of such compounds.
• My DIR hydroquinone compounds are also advantageously used in non-light-sensitive layers of a silver halide coating, e.g., interlayers, underlayers and overcoats, etc. i
• some of my photographic elements advantageously form diffusible dyes that are transferred during the development step to a mordanted reception sheet.
• the reception sheet for receiving the diffusible dye images can be an integral part of the photosensitive element.
• a typical element of this type can comprise a support (any of those mentioned previously), a mordanted hydrophilic colloid layer thereon and the various light-sensitive layers described above coated thereover. It is advantageous to have a stripping layer comprising a layer containing polyvinyl alcohol or an alkali-soluble cellulose ether phthalate vehicle, or a wet or dry stripping layer between the mordanted layer and the first layer of the light-sensitive element so that the reception sheet can be easily removed after development.
• the support is transparent, the light exposure can be made through it ifdesired.
• elements of this type which have the reception sheet as an integral part and which not only form the transfer images but also nondiffusible dye images, it is advantageous after development to provide the image-forming layers with a permanent support; this is advantageously done at the time the reception sheet is stripped off.
• a separate reception sheet is contacted with the outermost light-exposed light-sensitive layer of the photographic element in the presence of the developer solution and then separated after completion of development.
• mordant materials for acid dyes are advantageously used on the reception layer, including polymers of amino guanidine derivatives of vinyl methyl ketone described in the Minsk US. Pat. No. 2,882,156, issued Apr. I4, 1959 (which disclosure is incorporated herein by reference); the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al. US. Pat. No. 2,484,430, issued Oct. I I, I949 (which disclosure is incorporated herein by reference); and cetyl trimethylammonium bromide; etc.
• Particularly effective mordanting compositions are described in Knechel et al. US. Pat, No. 3,27l,l48 and Bush US. Pat. No. 3,27l,l47, both issued Sept. 6, I966 (which disclosures are both incorporated herein by reference).
• any of the well-known nondiffusible couplers which form diffusible dyes are used advantageously in my photographic elements.
• Typical examples include the couplers which form diffusible dyes upon color development as described in Barr et al. US. Pat. No. 3,227,551, issued .Ian. 4, I966 (which disclosure is incorporated herein by reference).
• Couplers I through X all react with oxidized primary aromatic amine colordeveloping agents to release diffusible yellow dyes and nondiffusing cyan dyes except VIII which forms a nondiffusible magenta dye and IX which forms a nondiffusible yellow dye, (ouplers XI to XXIX react with oxidized color-developing agent to form diffusible cyan dyes; Couplers XXX to XLI react with oxidized color-developing agent to form diffusible magenta dyes; and Couplers XLII to XLVI react with oxidized color-developing agent to form diffusible yellow dyes EXAMPLE 17 A photographic element is made like that described in example except that in addition to the coupler, 1-(2,4,6- trichlorophenyl)-3-pentadecyl-4-chloro-5-pyrazolone, coupler 1-(4-sulfophenyl )-3-( 4sulfoan
• a reception sheet comprising a cellulose acetate film support coated with a gelatin layer containing cetyl trimethylammonium bromide is moistened on the gelatin-mordant layer with the developer solution described in example 1 and this layer is firmly contacted with the outermost light-senisitve layer of the element until development is completed and then the reception sheet is separated from the developed element carrying in the mordanted layer a composite magenta dye image of the SLR latent image and cyan dye image of the MTl latent image.
• the developed photographic element has in it the silver and dye images described in example 1, and the processing of this element is completed as described in example 1.'
• the dye images in the reception sheet are ready for study as soon as the reception sheet is separated from the developed element, however, it is advantageous to remove residual developer solution from the reception sheet by any convenient method, e.g., water washing, squeezing, contacting with a dilute acid solution (e.g., dilute acetic acid solution), etc.
• EXAMPLE 18 A photographic element is made like that described in example except that coupler l-(4-sulfophenyl)-3-(4-sulfoanilino)-4-(3-octadecylcarbamylphenylthio)-5-pyrazolone disodium salt is used in the coarse grain blue-sensitive emulsion instead of coupler l-(2,4,6-trichlorophenyl)-3-pen tadecyl-4-chloro-5-pyrazolone, and coupler l-hydroxy-4-(3- oetadecylearbamylphenylthio)-N-ethyl-3 ,5 '-dicarboxy-2- naphthamide is used in the fine grain green-sensitized emulsion instead of coupler 2-[a-(3-pentadecylphenoxy)butyramido]-5 -methoxyphenol.
• the photographic element is exposed as described in example 1
• a photographic element capable of recording images 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 Sm to about 1,200 my. which silver halide emulsions will record,
• said second layer comprising a finer grained and more rapidly developing silver halide emulsion than the emulsion in said first lightsensitive layer, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer, a nondiffusible coupler that reacts with oxidized primary aromatic amine color-developing agent to form a dye, and contiguous to silver halide grains in said second light-sensitive layer a nondiffusible development inhibitor-releasing hydroquinone compound that cross-oxidizes with oxidized primary aromatic amine color developer to release a diffusible development-inhibiting agent, said development inhibitor having substantially no development-inhibiting effect on the silver halide development in the second light-sensitive layer but produces a substantial inhibitionof the development of the said silver
• a photographic camera speed element capable of recording images comprising a support having coated thereon:
• 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 mp to about 1,200 my and a nondiffusing coupler which reacts with an oxidized primary aromatic amine color-developing agent to form a nondiffusible dye
• a second light-sensitive hydrophilic colloid layer sensitive to at least one region of the said actinic spectrum that is different from the region of said actinic spectrum to which said silver halide emulsion in said first light'sensi tive layer is sensitive, said second layer comprising a finer grained and more rapidly developing silver halide emulsion than the emulsion in said first light-sensitive layer, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer, a nondiffusible coupler that reacts with oxidized primary aromatic amine color-developing agent to form a dye having a different color than the dye formed by the coupler in the said first light-sensitive layer, and contiguous to the said silver halide grains in said second light-sensitive layer a nondiffusi hle development inhibitor-releasing thioether hydroquinone compound that cross-oxidizes with an oxidized primary aromatic amine color developer to form a diffusible mercaptan development-inhibi
• a photographic element of claim 2 in which the nondiffusible development inhibitor-releasing thioether hydroquinone compound cross-oxidizes with an oxidized primary aromatic amine color-developing agent to form a diffusiblc heterocyclie mercapto development-inhibiting agent in which the heterocyclic ring has from four to six atoms in the ring with the heteroatoms being selected from the class consisting of nitrogen, oxygen, sullur and selenium such that the rmg has at least one nitrogen atom.
• a photographic element of claim 2 in which the nondiffusible development inhibitor-releasing thioether hydroquin one compound cross-oxidizes with an oxidized primary aromatic amine color-developing agent to form a heterocyclic mercapto development-inhibiting agent in which the heterocyclic ring has from four to six atoms in the ring with the heteroatoms being selected from the class consisting of nitrogen, oxygen, sulfur and selenium such that the ring has at least one nitrogen atom and in which the said first light-sensitive hydrophilic colloid layer is coated as the first light-sensr tive layer on the said support and the said second light-sensitive hydrophilic colloid layer is coated over the said first lightsensitive hydrophilic colloid layer.
• a photographic element of claim 2 in which the nondiffusible development inhibitor-releasing thioether hydroquinone compound cross-oxidizes with an oxidized primary aromatic amine color developing agent to form a diffusible heterocyclic mercapto development-inhibiting agent in which the heterocyclic ring has from four to six atoms in the ring with the heteroatoms being selected from the class consisting of nitrogen, oxygen, sulfur and selenium such that the ring has at least one nitrogen atom, and in which the said first light-sensitive layer and the said second light-sensitive layer are coated so that the said second light-sensitive layer is nearest the support and between the support and the said first light-sensitive layer.
• 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.
• 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 emulsion.
• 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.
• 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.
• a photographic element comprising a support coated in succession on one side with:
• a first light-sensitive hydrophilic colloid layer comprising a camera speed fine grain rapidly developing silver chlorobromide emulsion sensitive to at least one region of the visible spectrum and contiguous to the said silver chlorobromide emulsion, a first colorless nondiffusible coupler that forms upon reaction with oxidized primary aromatic amine color-developing agent during color development a nondiffusible dye, and a nondiffusible development inhibitor-releasing thioether hydroquinone compound which cross-oxidizes with oxidized primary aromatic amine color-developing agent to release a diffusible development-inhibiting agent which has substantially no effect on the development of the said silver chlorobromide in l 2.
• a second light-sensitive hydrophilic colloid layer comprising a camera speed coarse grain silver bromoiodide emulsion sensitive to at least one region of the visible spectrum that is different than for said silver chlorobromide emulsion in l) 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 halide iodide emulsion having a developing induction period such that sufficient 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 a third light-sensitive hydrophilit colloid layer comprising a fine grain rapidly developing silver chlorobromide emulsion sensitive to at least one region of the visible spectrum that is different from the regions that the silver halide emplsions in (l and (2) are sensitive
• 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 at least one 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 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 contiguous to said silver chlorobromide emulsion a nondiffusible thioether hydroquinone compound having the formula:
• Q is selected from the group consisting of the hydrogen atom and an alkaline splittable acyl masking group
• O is selected from the group consisting of the hydrogen atom and an alkaline splittable ACYL masking group
• S is a monothio connecting radical
• Rad is a heterocyclic radical which forms a mercaptan with said monothio connecting radical, said heterocyclic radical being selected from the class consisting of a 5- tetrazolyl group, a 2-benzoxazolyl group, a 2- benzothiazolyl group, a Z-oxadiazolyl group and a 2- thiadiazolyl group
• Ball is a photographically inert organic ballasting radical of such molecular size and configuration as to render said hydroquinone compound nondiffusible
• O is selected from the group consisting of the hydrogen atom, a SO M group and a COOM group
• M is an atom selected from the class consisting of hydrogen and an alkali metal.
• a photographic element comprising a support coated in succession with:
• a first light-sensitive gelatin layer comprising a green-sensitized coarse grain silver chlorobromoiodide emulsion and the nondiffusing magenta dye-forming coupler lphenyl-3- 3-[a-( 3-pentadecylphenoxy )acetamido] benzamido pyrazolone;
• a second light-sensitive gelatin layer comprising a redsensitized fine grain rapidly developing gelatino silver chlorobromide emulsion, the nondiffusing cyan dyeforming coupler, l-hydroxy-N-[6-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide and the development inhibitorreleasing hydroquinone compound 2- ⁇ 4-[3-(4-t-amyl-xsulfophenoxy)-benzamido]phenethyl ⁇ -x-( l-phenyl-S- tetrazolylthio)hydroquinone diaeetate sodium salt dihydrate.
• a photographic element comprising a support coated in succession with:
• 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-tirchlorophenyl)-3-pentadecyl-4-chloro-5 pyrazolone and 2.
• a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine grain rapidly developing gelatino silver bromoiodide emulsion, the cyan dye-forming coupler, 2-[a-(3-pentadecylphenoxy)butyramido1-5- methoxyphenol and the development inhibitor-releasing hydroquinone, 2- I [3-[ 5-( B-carboxypropionamido )-2- (2,4-di-t-amylphenoxy)benzamido]ethyl ⁇ -3,5-dimethyl- 6-(2-oxadiazolylthio)hydroquinone.
• a photographic element comprising a support coated in succession with:
• 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, 2-[a-(2,4-di-t-amylphenoxy)butylamido]4,6-dichloro-5methylphenol,
• a photographic element comprising a support coated in succession with:
• 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-tamylphenoxy)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 coupler, lphenyl3pentadecyl-S-pyrazolone and the DIR hydroquinone compound, 5-[4-(3,5-disulfobenzamido)phenethyl]-2-methyl-3-( l-phenyl-S- tetrazolylthio)hydroquinone disodium salt.
• a photographic element comprising a support having coated thereon:
• a first light-sensitive hydrophilic colloid layer comprising a silver halide emulsion sensitive to at least one region of the actinic spectrum
• a second light-sensitive hydrophilic colloid layer sensitive to at least one region of the actinic spectrum that is different from the region to which said first light-sensitive layer is sensitive, said second light-sensitive layer comprising a silver halide emulsion, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer a nondiffusible development inhibitor-releasing hydroquinone compound having the formuwherein Q is selected from the group consisting of the hydrogen atom and an alkaline splittable acyl masking group; 0 is selected from the group consisting of the hydrogen atom and an alkaline splittable acyl masking group; S- is a monothio connecting radical; Rad is a photographically inert diffusible radical that forms a mercaptan with said monothio connecting radical; Ball is a photographically inert organic ballasting radical of such molecular size and configuration as to render said hydroquinone compound nondiffusible; and O is selected from the group consisting of the hydrogen atom,
• a photographic element comprising the support having coated in succession on one side:
• a red-sensitive gelatino silver bromoiodide emulsion layer containing the development inhibitor-releasing hydroquinone compound 2- l4-[ 3-(4-t-amyl-x-sulfophenoxy)benzamido1-phenethyl]-x-( l-phenyl-S- tetrazolylthio)hydroquinone sodium salt and the nondif fusing cyan dye-forming coupler l-hydroxy-N-[6-(2A-dit-amylphenoxy)butyl]-2-naphthamide; and
• 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 imagewise 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 imagewise 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.
• 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 a nondiffusing coupler that forms a nondiffusing dye upon color development, and (b) a second light-sensitive hydrophilic colloid layer comprising a fine grain rapidly developing silver chlorobromide emulsion responsive only to the other of said light images and contiguous to the said silver chlorobromide emulsion a nondiffusible coupler that forms upon color development a nondiffusible dye having a different color than the dye formed by color development of the coupler in the said first layer and contiguous to the said silver chlorobromide emulsion a nondiffusible development inhibitor-releasing hydroquinone compound that cross-oxidizes with oxidized primary aromatic amine color-developing agent to release a diffusible development-inhibiting agent which
• 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 a nondiffusing coupler that forms a diffusing dye upon color development, and (b) a second light-sensitive hydrophilic colloid layer comprising a fine grain rapidly developing silver chlorobromide emulsion responsive only to the other of said light images and contiguous to the said silver chlorobromide emulsion a nondiffusible coupler that forms upon color development a difi'usible dye having a different color than the dye formed by color development of the coupler in the said first layer and contiguous to the said silver chlorobromide emulsion a nondiffusible development inhibitor-releasing hydroquinone compound that cross-oxidizes with oxidized primary aromatic amine color-developing agent to release a diffusible development-inhibiting agent which has substantially no

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• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (26)

Citations (3)

• 0
  • BE BE730884D patent/BE730884A/xx unknown
• 1968
  • 1968-04-01 US US717923A patent/US3620746A/en not_active Expired - Lifetime
• 1969
  • 1969-04-01 FR FR6909807A patent/FR2011487A1/fr not_active Withdrawn
  • 1969-04-01 GB GB06868/69A patent/GB1269072A/en not_active Expired

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