US3227552A - Preparation of photographic direct positive color images - Google Patents

Preparation of photographic direct positive color images Download PDF

Info

Publication number
US3227552A
US3227552A US392471A US39247164A US3227552A US 3227552 A US3227552 A US 3227552A US 392471 A US392471 A US 392471A US 39247164 A US39247164 A US 39247164A US 3227552 A US3227552 A US 3227552A
Authority
US
United States
Prior art keywords
color
radical
coupler
dye
silver halide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US392471A
Other languages
English (en)
Inventor
Keith E Whitmore
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE603747D priority Critical patent/BE603747A/xx
Priority to BE636671D priority patent/BE636671A/xx
Priority to FR861393A priority patent/FR1293709A/fr
Priority to DEE25335A priority patent/DE1167655B/de
Priority to GB33067/63A priority patent/GB1061294A/en
Priority to FR945633A priority patent/FR1373861A/fr
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US392471A priority patent/US3227552A/en
Application granted granted Critical
Publication of US3227552A publication Critical patent/US3227552A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01C—MEASURING DISTANCES, LEVELS OR BEARINGS; SURVEYING; NAVIGATION; GYROSCOPIC INSTRUMENTS; PHOTOGRAMMETRY OR VIDEOGRAMMETRY
    • G01C19/00—Gyroscopes; Turn-sensitive devices using vibrating masses; Turn-sensitive devices without moving masses; Measuring angular rate using gyroscopic effects
    • G01C19/02—Rotary gyroscopes
    • G01C19/40—Rotary gyroscopes for control by signals from a master compass, i.e. repeater compasses
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C5/3014—Hydrazine; Hydroxylamine; Urea; Derivatives thereof
    • 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
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
    • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/142—Dye mordant

Definitions

  • the present invention concerns color photography, and more particularly, photographic silver halide emulsions suitable for use in preparing direct positive color images and methods for processing such emulsions.
  • the invention includes color developing with an alkaline color developing composition containing an aromatic primary amino color developing agent photographic elements that contain at least one reversal silver halide emulsion wherein the silver halide forms latent images predominantly inside the silver halide grains when exposed to light.
  • a photographic color coupling material that forms a dye in the regions of development with oxidation product of the color developing agent is positioned contiguous to the silver halide of the emulsion.
  • the color development is carried out in the presence of a hydrazide or a hydrazone as described below to form a direct positive dye image, the hydrazide or hydrazone not comprising the dye image formed.
  • Sulfonated hydroquinones as described below are also useful addenda.
  • the reversal or direct-positive silver halide emulsions utilized in the photographic or light-sensitive elements of the invention are to be distinguished from emulsions containing silver halide grains that have substantial surface 3,227,552 Patented Jan. 4, 1966 sensitivity and form latent images when exposed to light on the surface thereof.
  • Suitable silver halides include silver bromide, silver bromoiodide, silver chloroiodide, and silver chlorobromoiodide.
  • Such emulsions are those which, when measured according to normal photographic techniques by coating a test portion of the emulsion on a transparent support, exposing to a light intensity scale having a fixed time between 1 10 and 1 second, bleaching 5 minutes in a 0.3% potassium ferricyanide solution at F. and developing for about 5 minutes at 65 F.
  • Developer B below an internal-type developer
  • Developer A below a surface-type developer
  • hydrophilic organic colloids can be utilized as the vehicle or carrier. It is preferred to utilize gelatin as the hydrophilic colloid or carrier material although such material as polyvinyl alcohol and its water-soluble derivatives and copolymers, water-soluble c-opolymers such as polyacrylamide, imm-idized polyacrylamide, etc.,
  • water-permeable coats such as colloidal albumin, watersoluble cellulose derivatives, etc.
  • colloidal albumin watersoluble cellulose derivatives, etc.
  • Compatible mixtures of two or more of such colloids can also be utilized.
  • hydrazides and hydrazones are nitrogen-containing compounds having the formulas wherein R is an aryl radical and including substituted aryl radicals; R is an acyl or a sulfonyl radical; and R is an alkylidene radical and including substituted alkylidene radicals.
  • Typical aryl radicals for the substituent R have the formula XR wherein R is an aryl radical and X can be such substituent-s as hydrogen, hydroxy, amino, alkyl, alkylamino, arylamino, heterocyclic amino (amino contains a heterocyclic moiety), alkoxy, aryloxy, acyloxy, arylcarbonamido, alkylcarbonamido, heterocyclic carbonamido (earbonamido contains a heterocyclic moiety),
  • Typical acyl and sulfonyl radicals for the substituent R have the formula wherein Y can be such substituents as alkyl, aryl and heterocyclic radicals. Z can represent a hydrogen atom or the same substituents as Y as well as radicals having the formula iOA to form oxalyl radicals wherein A is an alkyl, aryl or a heterOcycl-ic radical.
  • D can be a hydrogen atom or such radicals as alkyl, aryl and heterocyclic radicals.
  • Typical aryl substituents for the above-described hydrazides and hydrazones include phenyl, naphthyl, diphenyl, and the like.
  • Typical heterocyclic substituents for the above-described hydrazides and hydrazones include azoles, azines, furyl, th-iophene, quinoline, pyrazole, and the like.
  • Typical alkyl (or alkylene) substituents for the above-described hydrazides and hydrazones have 1 to 22 carbon atoms including methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, t-butyl, amyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl, n-eicosyl, ndocosyl, etc.
  • Illustrative specific hydrazides and hydrazones used in the invention include:
  • the amount of hydrazide or hydrazone utilized can be Widely varied, substantial amounts of such addenda not being objectionable.
  • the examples below illustrate the use of varying concentrations of such addenda for use in emulsions, developers and receiving layers.
  • concentrations of such addenda for use in emulsions, developers and receiving layers.
  • One skilled in the art could readily determine optimum concentrations for a particular color system.
  • I utilize between about 1 to 20 mg. of hydrazide or hydrazone addenda per square foot of each light-sensitive layer of the photoelement, or an equivalent amount in the receiving sheet, or about .1 to 2 grams of hydrazide or hydrazone addenda per liter of developer.
  • larger or smaller amounts are suitable.
  • Particularly useful photographic elements of the invention are those containing on the emulsion side of the support a substituted hydroquinone containing at least one sulfonic acid radical (SO H), including ammonium and alkali metal salts thereof.
  • SO H sulfonic acid radical
  • Such sulfonated hydroquinones cooperate with the above-described hydrazides and hydrazones to give increased color or dye yield, to wit, increased color D
  • Particularly useful sulfonated hydroquinones of the invention have the formulas OH OH i i R5 NH( i R or iNHR can be substituted, R and R for example suitably being aryl radicals such as phenyl and alkyl radicals as well as hydrogen atoms and sulfonic acid radicals.
  • the alkyl radicals can be substituted alkyl radicals and include aralkyl radicals.
  • the chain length or size of the alkyl, alkyleen and acylamino radicals can be widely varied depending on the degree of diffusibility desired, one skilled in the art readily being able to ascertain the amount of ballasting needed for a particular purpose.
  • Alkyl and alkylene radicals having 1 to 22 carbon atoms are suitable,
  • alkyl radicals having 8 to 22 carbon atoms and alkylene radicals having 1 to 8 carbon atoms are preferred.
  • Illustrative sulfonated hydroquinones used in the photographic elements of the invention include:
  • Optimum concentrations can be determined by one skilled in the art although I generally utilized about .1 to 10 mg, and preferably about .1 to 5 mg, of the sulfonated hydroquinone per square foot of each light-sensitive layer of the photoelement. However, larger or smaller amounts are suitable.
  • the photographic elements of the invention have incorporated contiguous to the silver halide grains of at least one silver halide emulsion layer a nondifiusible photographic color coupler that reacts with oxidized aromatic primary amino color developing agent to form a dye.
  • the couplers can be in the silver halide emulsion layer or in an adjacent layer. Suitable couplers are well known in the art and are generally 5-pyrazolone, phenolic or open-chain ketomethylene compounds.
  • nondiffusible couplers that form diffusible dyes on color development are referred to herein as DDR or dilfusible dye-releasing couplers.
  • DDR couplers are useful in preparing direct positive color diffusion transfer images in accordance with the invention.
  • Nondiffusible couplers that form nondilfusible dyes on color development can also be utilized to prepare direct positive images in accordance with the invention.
  • the DDR couplers are used in preparing photographic elements of the invention having utility in diffusion transfer processes, such couplers including those having the formulas DYE-LINK(COUP--BALL) and BALL-LINK( COUPSOL) n a wise to a reception layer.
  • I I (1) DYE is a dye radical containing an acidic solubilizing radical
  • COUP is a photographic color coupler radical such as a S-pyrazolone coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, the coupler radical being substituted in the coupling position with the connecting or linkage radical;
  • BALL is a photographically inert organic radical of such molecular size and configuration as to render the coupler nondilfusing in the element in the alkaline processing solution;
  • SOL is either a hydrogen atom or an acidic solubilizing group when the color developing agent contains an acidic solubilizing radical, SOL always being an acidic solubilizing radical when the color developing agent is free of an acidic solubilizing group;
  • n is an integer of l or 2 when LINK is an alkylidene radical, and n is always 1 when LINK is one of the other aforementioned connecting radicals, namely, azo, azoxy, mercuri, oxy, monothio, or dithio.
  • the acidic solubilizing radicals attached to the diffusible dye-releasing (DDR) couplers described above can be solubilizing radicals which when attached to the coupler or developer moieties of the dyes, render the dyes ditfusible in the element in alkaline processing solutions.
  • Typical of such radicals are carboxylic, sulfonic, ionizable sulfonamido, and hydroxy-substituted groups that lend to dyes negative charges.
  • Typical dye radical substituents (DYE) of the DDR couplers include azo, azomethine, indoaniline, indophenol, anthraquinone and related dye radicals well known in the art that exhibit selective absorption in the visible spectrum.
  • the dye radicals contain acidic solubilizin g moieties.
  • DDR couplers having the formula DYE- LINK(COUP-BALL) as described above are reacted With oxidized color developing agent, the connecting radical (LINK) is split and a diifusible preformed acid dye (DYE) is released which diffuses image- An acidic solubilizing group on the preformed dye lends ditfusibility and m'ordantability to the dye molecule.
  • the coupling portion of the DDR coupler (COUP) couples with color developing agent oxidation product to form a dye that is nonditfusible in the element because of the attached ballasting group (BALL) in a noncoupling position.
  • the color of the dilfusible dye is determined by the color of the preformed dye moiety (DYE), the color of the reaction product of color developer oxidation product and the coupler moiety (COUP) being unimportant to the color of the diffusible image.
  • the connecting radical (LINK) is split and a difi'usible dye is formed with the color developing agent oxidation product and the coupling portion (COUP) of the DDR coupled which diffuses imagewise to a reception layer. Diffusibility is imparted to the dye by an acidic solubilizing group attached to a noncoupling position of the coupling portion' 7 (COUP) of the DDR coupler or to the color developing agent.
  • the ballast portion of the DDR coupler remains immobile.
  • the color of the ditfusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COUP).
  • the coupler radical (COUP) in the DDR couplers is a S-pyrazolone radical
  • the coupler radical (COUP) in the DDR couplers is a cyanforming phenolic coupler radical
  • Rlfl COAT--12 wherein R is an alkyl group or a phenyl group.
  • BALLLINK--(COUP SOL) is an azo radical
  • the ballasting radical (BALL) be a phenyl redaical containing either a hydroxy group or an amino group (--NH substituted in the ortho or 2-position of the phenyl moiety.
  • ballast groups (BALL) in the DDR coupler compounds described above is not critical as long as they confer nondiifusibility to the coupler compounds.
  • Typical ballast groups exemplified hereinafter in the specific couplers disclosed include long chain alkyl radicals or several short chain alkyl radicals having e.g., 8 to 22 carbon atoms, linked directly or indirectly to the coupler molecules as well as aromatic radicals of the benzene and naphthalene series, etc., linked directly or indirectly to the coupler molecules by a splittable linkage, or by a removable or irremovable but otherwise nonfunctional linkage depending upon the nature of the coupler compound.
  • Useful ballast groups generally have at least 8 carbon atoms.
  • DDR couplers are known in the art. Typically suitable DDR couplers and methods for preparing such couplers are described in copending application Serial No. 222,105 filed September 7, 1962 and in the following patents: Canadian Patents 602,606 and 602,607; British Patents 840,731 and 904,364; French Patents 1,224,012, 1,291,110 and 1,293,709; and Belgian Patents 578,470, 591,444, 603,213, 603,747 and 625,137.
  • nondiffusible couplers that form nondiffusible dyes on color development are well-known in the art. Typical of such couplers are disclosed in the following patents: U.S. Patent 2,956,876 (column 5, lines 30 to 59); U.S. Patent 2,640,776; U.S. Patent 2,407,210 and U.S. Patent 2,474,293.
  • Couplers including a-naphthols, couple at the 4-position, open-chain ketomethylene couplers couple at the carbon atom forming the methylene moiety (e.g.,
  • nondiifusing and nondiffusible used herein as applied to couplers and dyes have the meaning commonly applied to the term in color photography and denoate 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 in the presence of aqueous alkaline processing compositions.
  • diffusing and diffusible as applied to the dyes released from the DDR couplers in the present processes and the developing agents have the converse meaning and denote materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of aqueous alkaline processing compositions.
  • the photographic elements of the invention are processed with alkaline compositions in the presence of an aromatic primary amino color developing agent, p-phenylenediamine developing agents being particularly useful.
  • the color developing agent can be either incorporated in an aqueous alkaline composition that is applied to the present photographic elements on processing or the color developing agent can be incorporated in the lightsensitive element.
  • Typical aromatic primary amino color developing agents include:
  • Schiifi bases are prepared by reacting primary amino developing agents with sulfonated, hydroxylated or carboxylated aromatic aldehydes of the benzene or naphthalene series.
  • a typical Schiff base color developing agent can be prepared by reacting 2-amino-5-diethylaminotoluene and o-sulfobenzaldehyde.
  • Schiif base developers that are useful as such, as salts or as sulfur dioxide complexes include:
  • Such incorporated developing agents can be activated by immersing the photographic element in an aqueous alkaline solution or by spreading an aqueous alkaline solution on the surface of the element.
  • Such incorporated developing agents can be positioned in any layer of the present photographic elements from which the developing agents can be readily made available for development on activation with aqueous alkaline solutions.
  • incorporated color developing agents are incorporated in layers contiguous to the light-sensitive silver halide emulsion layers, although the color developing agent can be utilized in the silver halide emulsion layers.
  • the reception layer used to receive the diffused dye images on color development when DDR couplers are used in the photoelements of the invention can be either a separate receiving sheet pressed in contact with the photoelement or a layer integral with the photoelement.
  • the development and transfer operations can be effected by bathing either or both the exposed photographic element and the mordanted reception sheet in the developing solution before rolling into contact with each other.
  • a viscous developing composition can be placed between the elements for spreading in a predetermined and amount across and in contact with the exposed surface of the sensitive element so as to provide all of the solution required for the picture area.
  • the viscous developing composition is desirably utilized in one or more pods or containers integral with the photographic element or the reception sheet that can be readily ruptured when development is desired, suitable viscous developer utilization techniques being disclosed in U.S.
  • Such processing techniques utilizing viscous processing compositions and rupturable pods can also be used to color develop photographic elements containing couplers that form nondiffusible dyes.
  • reception layer for receiving the difiusible dye is an integral part of the photosensitive assembly, it is also useful.
  • a typical element of this type can comprise a support, a mordanted colloid layer thereon and the various emulsion layers described above coated thereover.
  • easily dissolved emulsions such as those containing polyvinyl alcohol or alkali-soluble cellulose ether phthalate vehicles, or a wet or dry stripping layer containing such vehicles is provided between the emulsions and reception layer, the developed emulsion layers can then be readily separated from the reception layer leaving the dye image thereon.
  • the reception layer can be initially bonded to the outer emulsion surface. In this case, it is preferred to expose through the support of the senistive element unless the reception layer itself is transparent.
  • Such photoelements can be processed in the same manner as those not containing integral reception layers.
  • the dye reception layers used in the invention can contain any of the conventional mordant materials for dyes.
  • the reception layer can contain mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone described in U.S. Patent 2,882,156.
  • mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in U.S. Patent 2,484,430 and cetyl trirnethylammonium bromide, etc.
  • Particularly effective mordanting compositions are described in Belgian Patent 634,515.
  • mordanting compositions include at least one hydrophilic organic colloid containing a finely-divided, uniform dispersion of droplets or globules of a high-boiling, waterirnrniscible organic solvent in which is dissolved a high concentration of a cationic, nonpolymeric, organic dyemordanting compound for acid dyes.
  • Other mordanting compositions described in Belgian Patent 634,515 include at least one hydrophilic organic colloid containing a finelydivided, uniform dispersion of particles of a salt of an organic acidic composition containing free acid moieties and a cationic, non-polymeric, organic dye-mordanting compound for acid dyes.
  • reception layer or sheet can be sufficient by itself to mordant the dye as in the case of the use of a sheet or layer of a polyamide or related polymeric material.
  • Receiving sheets that release acidic material at a controlled rate such as are described in U.S. Patent 2,584,030 are useful.
  • Color developed photographic elements of the invention containing nondiffusible dye images on the support are treated after color development to remove silver in developed areas and to stabilize or fix silver halide in undeveloped areas.
  • the silver in the developed areas can be bleached from the element by any of the conventional techniques used in color photography such as with aqueous baths containing water-soluble ferricyanides, dichromates or the like bleach bath components.
  • the silver halide in the undeveloped areas can be stabilized or fixed by any of the conventional techniques used in silver halide photography including the use of aqueous baths containing silver halide solvents such as Water soluble thiosulfates and thiocyanates.
  • monobath compositions that can be utilized to both bleach and fix color developed photographic elements are useful.
  • Such blix baths contain as bleaching agents a complex salt of an alkali metal and trivalent iron with an organic acid having the formula radical, R to R being substituted or unsubstituted hydrocarbon residues and R also suitably being a hydrogen atom.
  • Such blix baths also contain known silver halide solvents such as water-soluble thiocyanates and thiosulfates.
  • such blix baths can contain watersoluble polyethylene oxides, or Water-soluble polyalkylene oxides wherein some of the oxygen atoms are replaced by sulfur atoms.
  • addenda have the formula Xl )m( )n( )m] wherein: R to R are bivalent organic radicals having 2 to 10 carbon atoms; In is an integer of 0 to n and p are integers of 1 to 100; Y is a radical having the formula -S, -4S
  • R being a lower aliphatic radical having 1 to 3 carbon atoms
  • X is a hydrogen atom or an aliphatic radical which can contain a substituent for improving the solubility of the compound (e.g., by hydroxyl, nitrile, amino, carboxylic acid or sulfonic acid groups or by a group of an acid of phosphorus).
  • X can also be an acyl radical derived from an aliphatic monoor dicarboxylic acid.
  • silver halide emulsions are preferably coated on photographic supports in the form of multilayer color photographic elements wherein at least three emulsion layers sensitive to different regions of the visible spectrum are coated on the support.
  • the uppermost light-sensitive emulsion layer is generally selectively sensitive to blue light
  • the next light-sensitive emulsion layer is generally selectively sensitive to green light
  • the lightsensitive emulsion layer nearest the support is generally selectively sensitive to red light.
  • a Carey Lea filter layer for absorbing blue radiation that may be transmitted through the uppermost blue sensitive layer.
  • the red, green and blue light-sensitive silver halide layers have contiguous to the silver halide a cyanforming, a magenta-forming and a yellow-forming coupler respectively, so that dyes substantially complementary to the color sensitivities or color of light recorded in the silver halide emulsions are formed on color development.
  • the physical disposition of the red, green and blue light-sensitive silver halide layers within the present photographic elements can be widely varied in accordance with usual practice.
  • Such multilayer photographic elements can also have other interlayers or sublayers for specialized purposes in accordance with usual practice;
  • Nondilfusing couplers that form nondiffusing dyes on reaction with oxidized color developing agents are desirably incorporated in interlayers of photographic elements of the invention used to prepare diffusion transfer multicolor images, such couplers serving to improve color separation by scavenging oxidized color developing agent that wanders out of the silver halide emulsion layer in which it was generated.
  • Reflection prints as well as transparencies can be prepared with photographic elements of the invention that contain couplers that form nondiffusible dyes on color development, white pigmented supports for the emulsion layers being suitably used for preparing reflection prints and transparent supports being suitably used for preparing transparencies.
  • a single layer light-sensitive element could be utilized to prepare fullcolor images.
  • Three types of packets of differently sensitized silver halide emulsions and their corresponding couplers for subtractive color photography can be incorporated into a single emulsion layer on a photographic support.
  • the photographic elements of the invention are useful for color-proofing a set of half-tone silver separation positives of the type commonly employed in the printing industry before making the final press plates.
  • three single color photographic elements containing silver halide that forms latent images inside the silver halide grains as described above can be typically employed wherein the elements contain nondifiusible couplers that form diifusible yellow, magenta and cyan dyes respectively when reacted with oxidized color developing agents.
  • Such a proofing process is carried out by exposing each of the single-color photographic elements through a silver image separation positive of the photographic record substantially complementary to the color of the diffusible dye formed by reacting the couplers in the respective photographic elements with development oxidation product of an aromatic primary amino color developing agent.
  • Each of the exposed elements is successively color developed in an aqueous alkaline color developing composition, and resulting dilfusible dyes successively transferred in register to a common recelving sheet for such dyes.
  • the exposures and dye transfers are carried out with the aid of mechanical registration means such as pins, pegs or the like.
  • the resulting three-color half-tone reproduction indicates the appearance of the final printed reproduction.
  • two color proofs can be prepared as Well as four-color proofs with photographic elements containing a coupler or more than one coupler that form diffusible black dyes on color development.
  • FIG. 1 of the drawings illustrates a typical single color photographic element of the invention wherein the dye-forming coupler is positioned in light-sensitive silver halide emulsion layer 11 coated on support 10. Over emulsion layer 11 is coated topcoat layer 12. Such an element is a singlecolor element and can be processed after exposure to prepare a direct positive color image by Wetting the exposed element with an aqueous processing solution containing an aromatic primary amino developing agent. If a DDR or diffusible dye-releasing coupler is used in emulsion layer 11, a receiving sheet having a reception layer which desirably contains a mordant is juxtaposed on topcoat layer 12 and the positive image formed when the DDR coupler reacts with oxidized color developing agent is allowed to diffuse and be transferred to the receiving sheet.
  • a dye image I 12 remains in layer 11 after color development which can thereafter be further processed to remove silver in exposed areas and silver halide in unexposed areas in the usual manner.
  • the feature hydrazides or hydrazones, or the sulfonated hy-droquinones can be positioned in either or both layers 11 and 12.
  • FIG. 2 illustrates a typical multicolor photographic element of the invention as well as a typical mordanted receiving sheet and a rupturable pod containing a processing composition that can be suitably utilized in conjunction with such a photographic element.
  • Coated on support 20 is red-sensitive emulsion layer 21 which contains a nonditfusible coupler that forms a cyan dye when reacted with oxidized color developing agent.
  • Over redsensitive emulsion layer 21 is coated interlayer 22 that serves to separate green-sensitive emulsion layer 23 a nd red-sensitive emulsion layer 21.
  • Interlayer 22 can contain such addenda as antioxidants, nondifi'usible couplers that react to form nonditfusible dyes with oxidized color developing agent from adjacent layers, filter dyes such as a magneta filter dye or the like.
  • Green-sensitive emulsion layer 23 contains a nondiffusible coupler that forms a magneta dye on color development.
  • interlayer 24 that serves to separate green-sensitive emulsion layer 23 and bluesensitive emulsion layer 25.
  • Interlayer 24, like interlayer 22 can contain anti-oxidants, nondilfusible couplers that react to form nondiffusible dyes with oxidized color developing agent from adjacent layers, filter dyes and the like.
  • Interlayer 24 typically contains yellow Carey Lea silver to serve as a filter for blue light.
  • Blue-sensitive emulsion layer 25 contains a nondiffusible coupler that forms a yellow dye on reaction with oxidized color developing agent.
  • topcoat layer 26 that typically contains such addenda as antioxidants, ultraviolet absorbers and the like.
  • the above-described sulfonated hydroquinones can be utilized in any of the layers 2146.
  • FIG. 2 is also illustrated a receiving sheet that can be used to receive dye images when DDR couplers are utilized in emulsion layers 21, 23 and 25.
  • the receiving sheet comprises support 28 having coated thereon mordant layer 27 and affixed thereto rupturable pod 29 containing processing solution.
  • Such processing solution is typically an aqueous alkaline material and can contain an aromatic primary amino color developing agent and a fogging agent if such are not incorporated in the light-sensitive element.
  • Lightsensitive layers 21, 23 and 25 are direct positive silver halide emulsion layers wherein the silver halide grains have a substantial amount of sensitivity internal to the grains. When such emulsions are processed, they develop in positive image areas or unexposed areas. Accordingly, in the processing of an exposed photographic element of the type described in FIG. 2 of the drawings, development occurs in the unexposed areas and resulting oxidized color developing agent reacts with the color couplers in the respective red, green, and blue sensitive layers to form cyan, magenta, and yellow dyes respectively.
  • a predominant proportion of the resulting oxidation product of the color developing agent is retained in the photographic element during the color development.
  • coupler-s that form dyes that are substantially complementary to the color of light recorded in the silver halide contiguous to the couplers are more generally used.
  • the feature hydrazides and hydrazones described above can be utilized in any layers 21-26 of the photographic element, in the alkaline processing composition of pod 29, or in mordant layer 27 of the receiving sheet.
  • Example 1 A color film was prepared by coating the following photographic gelatine-silver halide emulsion over an area of 720 square feet on a cellulose acetate film support:
  • a similar color film was prepared except that the methenol solution of the hydrazide was omitted for purposes of comparison.
  • the color films were then exposed for second with a 500 watt positive lamp and a 4.08 Corning filter on an Eastman Type 113 intensity scale sensitometer and thereafter developed in the viscous developer described below, Developer C.
  • the developing was carrier out by pressing the viscous developer between the color film samples and photographic image receiving sheets containing a cationic mordant at a thickness of .004 inch for 3 minutes at about 68 F.
  • the color films were then separated from the receiving sheets leaving positive cyan images on the rerxziving sheets.
  • the receiving sheet prepared from the color film containing the 5-(l-carbo-Z-phenylhydrazino)-1-phenyl-3-pyrazolidone had a positive cyan dye image having a substantially higher density than the receiving sheet prepared from the control color film containing no hydrazide as summarized by the data set out in Table A below.
  • the hydrazide emulsion addenda not only give improved dye density in accordance with the invention, but also particularly uniform transfers of diifusible dyes to receiving layers in diffusion transfer processes as described in Example 1.
  • related hydrazines such as phenyl hydrazine are utilized in the color developer, small bubbles form which result in nonuniform transfers of dyes to receiving sheets in diffusion transfer processes.
  • Example 2 A color film was prepared by coating the following photographic gelatine-silver halide emulsion over an area of 720 sq. ft. on a cellulose acetate film support:
  • Example 3 A color film was prepared by coating the following photographic gelatine-silver halide emulsion over an area of 720 sq. ft. on a cellulose acetate film support:
  • Example 4 A photographic gelatin-silver chlorobromoiodide emulsion having high internal sensitivity and low surface sensitivity was prepared by the procedure described in Davey et al., U.S. Patent 2,592,250, issued April 8, 1952. The emulsion was separated into several portions and various color couplers and the hydrazide, 1-[2-(2-4-di-t-amylphenoxy)-5-(3,5-disulfobenzoamido)benzoyl] 2 phenylhydrazide, were added to the emulsion portions. For determining the eiTect of the hydrazide addendum, emulsion portions containing no hydrazide were also prepared.
  • Each emulsion portion was coated on a cellulose acetate support at a coverage of mg. of silver, 200 mg. of gelatin, 100 mg. of coupler and 5 mg. of the hydrazide per sq. ft.
  • the resulting color films were then exposed on an intensity scale sensitometer as described in Example 1, processed by dipping for 5 seconds with a mordanted receiving sheet in Developer D described below and then pressed into contact with receiving sheets for periods of 4 minutes at about 20 C. Thereafter the receiving sheet was removed and the dye density of the positive image on the receiving sheet determined.
  • the improved dye densities resulting from the hydrazide emulsion addendum are summarized by the data set out in Table D below.
  • a film was P e as described in Example 4 (1) An emulsion optically sensitized to red light-containeohtalhlhg the eyah'fomhhg coupler, Y ing silver chlorobromoiodide at a coverage of 50 mg. A' Y P Y) P h at a of silver per square foot, gelatin at a coverage of 200 erege 50 P e the hydrezlde, mg.
  • Patent 2,592,250, yellow-forming couplers of Example 4 were incorporated Issued Apnl 5
  • the hhhs W then exposed 115mg individually in the prepared single color films.
  • the reneutral density p tablet in an Eastman 1B 8611- sulting color films were exposed on an intensity scale seneltometer and Processed as follows: sitometer as described in Example 1.
  • Each of the 70 Wash "min” 2 color fi.rns were developed with and without 0.3 g.
  • DEVELOPER F 4-amino-Nethyl-3-methyl-N-13 methylsultonamidoethylaniline g 10.0 Benzyl alcohol ml 10.0 Sodium sulfite 2.0 Trisodiurn phosphate 40.0 Sodium hydroxide 5.0 6-nitrobenzimidazole 0.05 Water to make one liter.
  • Example 8 Multilayer photographic elements suitable for use in preparing three-color diffusion transfer images were prepared by coating on cellulose acetate film supports the following layers numbered in sequence from the support (see FIG. 2 of the drawings):
  • the silver chlorobromoiodide utilized in layers 1, 3 and 5 was of the internal image type having high internal sensitivity and low surface sensitivity and prepared by the procedure described in Davey et al., US. Patent 2,592,- 250, issued April 8, 1952.
  • a similar multilayer photographic element as described above was prepared except that the hydrazide, 1-[2 (2,4 di t amylphenoxy)- 5 (3,5 disultobenzamid0)benzoyl] 2 phenylhydrazide, was utilized in layers 1, 3 and 5 of the element at coverages of 5.0 mg. per square foot in each of such layers.
  • the prepared photographic elements were then exposed in an intensity scale sensitometer as described in Example 1 and developed in Developer I below.
  • the :processing of the multilayer photographic elements was carried out by immersing for 20 seconds at 68 F. the elements and photographic image receiving sheets containing the cationic mordant, dimethyl-fl-hydroxyethylu-(octadecylamido)-propyl ammonium dihydrogen phosphate, bringing the photographic elements and receiving sheets in intimate contact for 5 minutes, and then separating the photographic element and the receiving sheet to produce a positive full-color image on the receiving sheet.
  • the increased values of the color D (measured on a Kodak Model 31A Densitometer) on the receiving sheet resulting trom the use of the hydrazide in the lightsensitive emulsions are summarized by the data set out in Table I below.
  • the hydrazide emulsion addenda used in this example was prepared by the following procedure. To a solution prepared from 27 g. of phenylhydrazine, 21 g. of sodium acetate, and 1 liter of glacial acetic acid was added 102 g. of 2-(2,4-ditertiary amylphenoxy) 5 nitrobenzoyl chloride (see procedure for compound 6, US. Patent 2,511,231) dissolved in 500 ml. of glacial acetic acid. The resultant mixture was stirred for one-half hour, then filtered. The filtrate was poured into 4 liters of water yielding a brown solid. The product was dried and crystallized from ligroin yielding 70 g.
  • Example 9 Multilayer photographic elements as described in Example 8 were processed in the presence of several hydrazides in the developer in lieu of their use in the lightsensitive emulsions. The photographic elements were then processed as described in Example 8 and positive full-color images transferred to the receiving sheet except that Developer J below was used as the developer.
  • the D and the D for the transferred dyes were determined as described in Example 8 and are summarized by the data set out in Table I and K below.
  • the amounts of hydrazide indicated in the tables refer to the amount added per liter of Developer I.
  • a similar photographic element was prepared for purposes of comparison without the hydrazide emulsion.
  • the photographic elements were processed and color images transferred to receiving sheets by the general method described in Example 8.
  • the processing cycle comprised a 10 second dip of the photographic elements and the receiving sheets in Developer K below bringing the photographic elements and receiving sheets in intimate contact for 5 minutes at E, and then separating the photographic elements from the receiving sheets to exhibit positive full-color images on the receiving sheets.
  • the increased value of the color D resulting from the coating containing the hydrazide is pointed-up by the data summarized in Table L below.
  • Example 11 Multilayer photographic elements as described in Example 8 were processed in the presence of several hydrazones in gelatin top-coats on the receiving sheets used to receive the color images.
  • the hydrazones were prepared by reacting the hydrazine, p-(fi-methylsulfonamidoethyl)phenyl hydrazine, with various aldehydes. More specifically, to ml. of 2.5% gelatin solution was added 100 mg. of p-(fi-methylsulfonamidoethyl)phenyl hydrazine. To this solution was added 2.5 ml. oxyguar gum solution (0.35% aldehyde).
  • hydrazone-containing solution was then coated on a mordanted receiving sheet as described in Example 8 at a coverage of 100 mg. of gelatin per square foot and 10 mg. of hydrazine (as a hydrazone) per square foot.
  • other hydrazones were prepared by substituting 2.5 ml., 5.0 ml. and 10.0 ml. portions of formalin, as well as sufiicient mucochloric acid and benzaldehyde to react the hydrazine, for the oxyguar gum.
  • the photographic elements were exposed in an intensity scale sensitometer as described in Example 1, immersed in Developer L described below for about 10 seconds at about 70 F. with the hydrazone-containing receiving sheet, and thereafter the photographic elements and the receiving sheets were brought into intimate contact for 5 minutes at about 70 F.
  • the receiving sheets and the photographic elements were then separated to yield positive full-color images on the receiving sheets.
  • the process was carried out without a hydrazone in the receiving sheet.
  • the increased values of the color D on the receiving sheets resulting from the use of the hydrazones in the receiving sheet are summarized by the data set out in Table M below. Similar results are obtained when hydrazones are utilized in the light-sensitive emulsions of the photographic element.
  • Example 12 The process of Example 11 was repeated except that oxalyl esters of phenylhydrazine in carboxymethyl cellulose topcoats were used in lieu of the hydrazones in gelatin topcoats for the receiving sheets.
  • the photographic elements were exposed and processed as described in Example 11 except that Developer M below was used as the developer.
  • the improved color densities of the dyes on the receiving sheets are summarized by the data set out in Table N below.
  • Example 13 The etfect of a sulfonated hydroquinone in a photographic element is illustrated by this example.
  • Two multilayer color photographic elements of the type described in Example 8 containing the hydrazide in each of the silver halide emulsion layers were prepared except that the sulfonated hydroquinone, 2,5-dihydroxy-4-octadecylbenzene sulfonic acid potassium salt, was omitted from one photographic element and was utilized in the three silver halide emulsion layers of the other at a coverage of 1.0 mg. per square foot.
  • the coatings were exposed and processed as described in Example 8.
  • the coatings were exposed and processed as described in Example 8. The
  • TAB LE 0 Dam of Transferred Dye Sulfouated Hydroquinone Red Green Blue Absent Present Example 14 This example illustrates that the addition of a sulfonated hydroquinone to a photographic element not containing a feature hydrazide or hydrazone of the invention imparts little or no improvement to the D of the transferred color image, particularly in the red and green.
  • a series of multilayer photographic elements of the type described in Example 8 were prepared, except that the hydrazide was omitted from each silver halide emulsion layer and the sulfonated hydroquinone, 2,5-dihydroxy-4- octadecyl-benzene sulfonic acid potassium salt, was utilized in various concentrations in each of such emulsion layers.
  • the photographic elements were exposed and processed as described in Example 10.
  • the D of the transferred positive dye images for the various concentrations of sulfonated hydroquinone are set out in Table P below.
  • Example 15 This example illustrates the advantages of utilizing a sulfonated hydroquinone in a photographic element of the invention containing a hydrazide and a nondiflusible coupler that forms a nonditfusible dye.
  • a multicolor photographic element was prepared by coating on a polyethylene-coated paper support the following layers numbered in sequence from the support:
  • a photographic element of the type described above was prepared except the sulfonated hydroquinone, 2-(2-octadecyl)-5-(2-sulfo-tert.-buty1)hydroquinone was omitted from the silver halide emulsion layers.
  • the photographic elements were then exposed in an intensity scale Eastman Ib sensitometer as described in Example 1 and processed as follows:
  • Another bleach-fix bath that can be suitably utilized has the following composition:
  • Example 16 Nonsulfonated hydroquinones do not cooperate with hydrazides and hydrazones in the processing of the photographic elements of the invention as do the feature sulfonated hydroquinones, such being illustated in this example.
  • Two photographic elements were prepared as described in Example 15 except that in each of the silver halide emulsion layers either the sulfonated hydroquinone, 2-(2-octadecyl)-5-(2-sulfo-tert. butyl)hydroquinone, or the nonsulfonated hydroquinone, 2,5-(di-iso-octyl)hydroquinone, were utilized at a coverage of 7 mg. per square foot.
  • the photographic elements were exposed as described in Example 15 and processed as follows:
  • Process step F. Time, min. Develop (Developer 0) 6 First fix 3 Wash 3 Bleach 3 Wash 11 Second fix 3 Wash 5 Butfer 2
  • the D values of the resulting positive color images are set out in Table R below.
  • DEVELOPER 0 (Same as Developer N of Example 15 plus 15 mg. per liter of p-methyl sulfonamide ethyl phenyl hydrazine.)
  • Buffer Citric acid g 10.79 Sodium citrate 2 6.00 Boric anhydride g 5.37 Sodium benzoate g 0.50 Zinc sulfate g 5.00 Water liter 1 pH 3.0.
  • Example 1 7 The photographic elements of the invention can be utilized to make color proofs from silver half-tone separation positives by successively transferring in register onto a receiving sheet a plurality of dye images as described in this example.
  • Three single-color photographic elements or matrices i.e., a yellow dye-forming matrix, a magenta dye-forming matrix and a cyan dye-forming matrix
  • a polyethylene coated paper support having coated thereon a photographic silver halide emulsion layer corresponding to layers 1, 3 and 5 respectively of the photographic element described in Example 8, except that the silver chlorobromoiodide was coated at a coverage of 60 mg. of silver per square foot, the gelatin was coated at a coverage of 100 mg.
  • the present invention thus provides new processes in the color photographic art and new photographic elements useful in such processes.
  • R is selected from the group consisting of an acyl radical and a sulfonyl radical
  • R is an alkylidene radical.
  • a photographic element as described in claim 1 wherein the coupler is a nondiifusible coupler capable of forming a nonditfusible dye with the development oxidation product of the color developing agent.
  • a photographic element as described in claim 1 wherein the coupler is a nondifiusible coupler capable of forming a difiusible dye with the development oxidation product of the color developing agent.
  • a photographic element as described in claim 7 wherein the nitrogen-containing compound is 1-phenylacetyl-Z-phenyhydrazide.
  • a photographic element as described in claim 11 wherein the nitrogen-containing compound is l-formyl-Z- phenylhydrazide.
  • a photographic element as described in claim 7 wherein the nitrogen-containing compound is 1-lauroyl-2- phenylhydrazide.
  • a photographic element as described in claim 7 wherein the nitrogen-containing compound is 1-acetyl-2- ⁇ 4 [2 (2,4 ditertiaryamylphenoxy) 5 (3,5 disulf Plumbingzamido benzamido phenyl ⁇ hydrazide.
  • a photographic element as described in claim 10 wherein the nitrogen-containing compound is 1-[2-(2,4- ditertiaryamylphenoxy) 5 (3,5 disulfobenzamido) benzoyl] -2-phenylhydrazide.
  • a light-sensitive photographic element comprising a support with superposed red, green and blue light-sensi tive direct positive silver halide emulsion layers wherein the silver halide forms latent images predominantly inside the silver halide grains, integral with said element and contiguous to said emulsion layers, respectively, a cyan dye-forming coupler, a magenta dye-forming coupler and a yellow dye-forming coupler, and a nitrogen-containmg compound having a formula selected from the group consisting of (1)
  • R is an aryl radical
  • R is selected from the group consisting of an acyl radical and a sulfonyl radical
  • R is an alkylidene radical
  • couplers being nondiffusible during development in an alkaline color developing composition containing an aromatic primary amino color developing agent, capable of forming diffusible acid dyes in said alkaline color developing composition by reaction with oxidation product of said color developing agent and having a formula selected from the group consisting of DYELINK COUP-BALL) n and BALL LINK (COUPSOL) wherein:
  • (l) DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group
  • (2) LINK is a connecting radical selected from the group consisting of an azo radical, an azoxy radical, a mercuri radical, an oxy radical, an alkylidene radical, a monothio radical and a dithio radical;
  • COUP is a coupler radical selected from the group consisting of a S-pyrazolone coupler radical, a'phenolic coupler radical, and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;
  • BALL is a photographically inert organic ballasting radical having at least 8 carbon atoms and of such molecular size and configuration as to render said couplers nondilfusible during development in said alkaline color developing solution;
  • SOL is selected from the group consisting of a hydrogen atom and an acidic solubiliziug group when said color developing agent contains an acidic solubilizing group, and SOL is an acidic solubiliziug group when said color developing agent is free of an acidic solubiliziug group;
  • n is an integer of 1 to 2 when said LINK is an alkylidene radical, and n is 1 when said LINK is a radical selected from the group consisting of an azo radical, an azoxy radical, a mercuri radical, an oxy radical, monothio radical, and dithio radical.
  • R is selected from the group consisting of an alkyl radical, an acylamino radical, a hydrogen atom and a sulfonic acid radical,
  • R is selected from the group consisting of an alkylene radical and an acylamino radical
  • R is selected from the group consisting of an alkyl radical and an acylamino radical
  • R is an aryl radical
  • R is selected from the group consisting of an acyl radical and a sulfonyl radical
  • R is an alkylidene radical.
  • a photographic process for preparing direct positive color images which comprises color developing with an alkaline color developing composition containing an aromatic primary amino color developing agent an imageexposed photographic element containing a silver halide direct positive emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains and a nondiffusible photographic color coupler capable of forming a dye when reacted with resulting development oxidation product of said color developing agent integral with said photographic element and continguous to said silver halide, said coupler reacting with said oxidation product to form a dye in regions of development, and said color developing being carried out with said developing composition in the presence of a nitrogencontaining compound having a formula selected from the group consisting of R-NHNH-R wherein:
  • R is an aryl radical
  • R is selected from the group consisting of an acyl radical and a sulfonyl radical, and (3) R is an alkylidene radical.
  • a photographic process for preparing direct positive color images which comprises color developing with an alkaline color developing composition containing an aromatic primary amino color developing agent an imageexposed photographic element containing a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains and a nondifiusible photographic color coupler capable of forming a dye when reacted with resulting development oxidation product of said color developing agent integral with said photographic element and continguous to said silver halide, said coupler being selected from the group consisting of a S-pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, said coupler reacting with said oxidation product to form a dye in regions of development, and said color developing being carried out in the presence of a nitrogen-containing compound having the formula RNHNHR wherein R is an aryl radical and R is selected from the group consisting of an acyl radical and a sulfonyl radical.
  • a color photographic ditfusion transfer process which comprises exposing a light-sensitive photographic element comprising a support having superposed thereon red, green and blue light-sensitive direct positive silver halide emulsion layers wherein the silver halide forms latent images predominantly inside the silver halide grains, integral with said element and contiguous to said emulsion layers, respectively, a cyan dye-forming coupler, a magenta dye-forming coupler and a yellow dye-forming coupler, said couplers being nondifiusible during development in an alkaline color developing composition containing an aromatic primary amino color developing agent, capable of forming diffusible acid dyes in said alkaline color developing solution by reaction with oxidation product of said color developing agent and having a formula selected from the group consisting of DYELINK(COUP-BALL) and BALLLINK COUPSOL) wherein:
  • (l) DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group
  • (2) LINK is a connecting radical selected from the group consisting of an azo radical, an azoxy radical, a mercuri radical, an oxy radical, an alkylidene radical, a monothio radical and a dithio radical;
  • COUP is a coupler radical selected from the group consisting of a -pyrazolone coupler radical, a phenolic coupler radical, and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;
  • BALL is a photographically inert organic ballasting radical having at least 8 carbon atoms and of such molecular size and configuration as to render said couplers nondiffusible during development in said alkaline color developing solution;
  • SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said color developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when said color developing agent is free of an acidic solubilizing group;
  • n is an integer of 1 to 2 when said LINK is an alkylidene radical, and n is 1 when said LINK is a radical selected from the group consisting of an azo radical, an azoxy radical, a mercuri radical, an oxy radical, a monothio radical, and a dithio radical;
  • R is an aryl radical
  • R is selected from the group consisting of an acyl radical and a sulfonyl radical
  • R is an alkylidene radical.
  • a photographic process for preparing direct positive color images which comprises color developing with an alkaline color developing composition containing an aromatic primary amino color developing agent an imageexposed photographic element containing (a) a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains, (b) a nonditfusible photographic color coupler capable of forming a dye when reacted with resulting development oxidation product of said color developing agent integral with said photographic element and contiguous to said silver halide, and (c) a sulfonated hydroquinone on the emulsion side of the photographic element having a formula selected from the group consisting of R S 0 H and wherein (1) R is selected from the group consisting of an alkyl radical, an acylamino radical, a hydrogen atom and a sulfonic acid radical,
  • R is selected from the group consisting of an alkylene radical and an acylamino radical
  • R is selected from the group consisting of an alkyl radical and an acylamino radical
  • R is selected from the group consisting of an acyl radical and a sulfonyl radical
  • R is an alkylidene radical.
  • a photographic proofing process which comprises exposing a plurality of single-color photographic elements as described in claim 4 to silver image separation positives of a multicolor photographic record substantially complementary in color to the ditlusible dye formed by color developing the respective elements in an alkaline composition containing an aromatic primary amino color developing agent, successively color developing the photographic elements with said alkaline composition, and successively transferring in register resulting diffusible dyes to a juxtapositioned receiving sheet to produce a positive multicolor image on said receiving sheet' 28.
  • R is selected from the group consisting of an alkylene radical and an acylamino radical
  • R is selected from the group consisting of an alkyl radical and an acylamino radical.
  • a photographic element comprising a support having coated thereon a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains containing a nondiffusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent, 1-formyl-2-phenylhydrazide at a coverage of about 1 to 20 mg. per square foot and 2,5-dihydroxy-4-octadecylbenzene sulfonic acid at a coverage of about .1 to 10 mg. per square foot.
  • a photographic element comprising a support having coated thereon a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains containing a nondiifusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent, 1 [2-(2,4-di-t.-amylphenoxy)-5-(3,5-disultobenzamido)benzoyl]-2-phenylhydrazide at a coverage of about 1 to 20 mg. per square foot and 2,5-dihydroxy-4-octadecylbenzene sulfonic acid at a coverage of about .1 to 10 mg. per square foot.
  • a photographic direct positive silver halide emulsion wherein the silver halide forms latent images predominantly inside the silver halide grains, said emulsion containing a non-difiusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline developing composition, and a nitrogen-containing compound having a formula selected from the group consisting of wherein:
  • R is an aryl radical
  • R is selected from the group consisting of an acyl radical and a sulfonyl radical, and (3) R is an alkylidene radical.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Radar, Positioning & Navigation (AREA)
  • Remote Sensing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US392471A 1960-05-13 1964-08-27 Preparation of photographic direct positive color images Expired - Lifetime US3227552A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BE603747D BE603747A (de) 1960-05-13
BE636671D BE636671A (de) 1960-05-13
FR861393A FR1293709A (fr) 1960-05-13 1961-05-10 Nouveau produit photographique en couleurs et procédé de reproduction photographique utilisant un tel produit
DEE25335A DE1167655B (de) 1960-05-13 1963-08-13 Verfahren zur Herstellung von farbigen Direktpositivbildern mit Hilfe einer Farbkuppler enthaltenden Direktpositivhalogensilberemulsion und photographisches Material hierfuer
GB33067/63A GB1061294A (en) 1960-05-13 1963-08-21 Photographic colour reproduction processes
FR945633A FR1373861A (fr) 1960-05-13 1963-08-26 Nouveau procédé de reproduction photographique en couleurs
US392471A US3227552A (en) 1960-05-13 1964-08-27 Preparation of photographic direct positive color images

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US2907560A 1960-05-13 1960-05-13
US22002862A 1962-08-28 1962-08-28
US392471A US3227552A (en) 1960-05-13 1964-08-27 Preparation of photographic direct positive color images

Publications (1)

Publication Number Publication Date
US3227552A true US3227552A (en) 1966-01-04

Family

ID=27363397

Family Applications (1)

Application Number Title Priority Date Filing Date
US392471A Expired - Lifetime US3227552A (en) 1960-05-13 1964-08-27 Preparation of photographic direct positive color images

Country Status (4)

Country Link
US (1) US3227552A (de)
BE (2) BE636671A (de)
DE (1) DE1167655B (de)
GB (1) GB1061294A (de)

Cited By (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330655A (en) * 1963-09-20 1967-07-11 Eastman Kodak Co Preparation of photographic direct positive color images
US3351465A (en) * 1962-12-28 1967-11-07 Polaroid Corp Photographic diffusion transfer processes utilizing a processing composition containing potassium and lithium ions
US3352672A (en) * 1964-04-09 1967-11-14 Eastman Kodak Co Photographic direct positive color process and element
DE2020814A1 (de) * 1969-04-28 1970-11-12 Eastman Kodak Co Photographisches Aufzeichnungsmaterial
US3620747A (en) * 1968-05-20 1971-11-16 Eastman Kodak Co Photographic element including superimposed silver halide layers of different speeds
FR2128801A1 (de) * 1971-03-11 1972-10-20 Eastman Kodak Co
US3793027A (en) * 1971-03-26 1974-02-19 Fuji Photo Film Co Ltd Developing composition for use with photographic materials for the graphic arts
US3942987A (en) * 1973-02-12 1976-03-09 Eastman Kodak Company Photographic materials with ballasted, alkali cleavable azo dyes
USRE28760E (en) * 1968-05-20 1976-04-06 Eastman Kodak Company Photographic element including superimposed silver halide layers of different speeds
US3954476A (en) * 1974-02-05 1976-05-04 Eastman Kodak Company Diffusable dye-releasing compounds which are cleavable upon oxidation
US3984245A (en) * 1973-10-09 1976-10-05 Fuji Photo Film Co., Ltd. Photographic sensitive materials
US4031127A (en) * 1975-08-06 1977-06-21 Eastman Kodak Company Acyl hydrazino thiourea derivatives as photographic nucleating agents
US4030925A (en) * 1975-08-06 1977-06-21 Eastman Kodak Company Photographic compositions and elements including internal latent image silver halide grains and acylhydrazinophenylthiourea nucleating agents therefor
US4030920A (en) * 1976-04-12 1977-06-21 Eastman Kodak Company Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement
US4080207A (en) * 1976-06-29 1978-03-21 Eastman Kodak Company Radiation-sensitive compositions and photographic elements containing N-(acylhydrazinophenyl) thioamide nucleating agents
JPS5384714A (en) * 1976-12-30 1978-07-26 Fuji Photo Film Co Ltd High sensitivity and high contrast photographic material
US4139387A (en) * 1977-10-19 1979-02-13 Agfa-Gevaert Aktiengesellschaft Process for the production of direct-positive photographic images
US4141730A (en) * 1975-04-08 1979-02-27 Fuji Photo Film Co., Ltd. Multilayer color photographic materials
US4166742A (en) * 1976-10-18 1979-09-04 Fuji Photo Film Co., Ltd. Contrasty light-sensitive silver halide material containing a hydrazine derivative and a heterocyclic mercaptan
US4266013A (en) * 1977-11-28 1981-05-05 Fuji Photo Film Co., Ltd. Direct positive silver halide light-sensitive material and method of forming direct positive image
US4268621A (en) * 1978-07-29 1981-05-19 Konishiroku Photo Industry Co., Ltd. Direct positive photographic material
US4268606A (en) * 1974-02-05 1981-05-19 Eastman Kodak Company Azo dye compounds and photographic materials
US4279987A (en) * 1978-11-14 1981-07-21 Konishiroku Photo Industry Co., Ltd. Light-sensitive, direct positive silver halide photographic material
US4306016A (en) * 1980-10-16 1981-12-15 Eastman Kodak Company Photographic emulsions and elements capable of forming direct-positive images
US4306017A (en) * 1980-11-17 1981-12-15 Eastman Kodak Company Photographic emulsions and elements capable of forming direct-positive images
US4315986A (en) * 1980-11-10 1982-02-16 Eastman Kodak Company Photographic emulsions and elements capable of forming direct-positive images
JPS57150845A (en) * 1981-03-13 1982-09-17 Fuji Photo Film Co Ltd Silver halide photographic material
US4374923A (en) * 1980-11-19 1983-02-22 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic light-sensitive material
US4377634A (en) * 1977-09-06 1983-03-22 Fuji Photo Film Co., Ltd. Method for forming high contrast photographic image
US4386149A (en) * 1978-02-28 1983-05-31 Ciba-Geigy Ag Process for the production of photographic images by dye diffusion transfer and photographic material suitable in this process
US4459347A (en) * 1983-05-11 1984-07-10 Eastman Kodak Company Adsorbable arylhydrazides and applications thereof to silver halide photography
DE3413049A1 (de) * 1983-04-07 1984-10-11 Fuji Photo Film Co., Ltd., Minamiashigara, Kanagawa Photographisches element fuer farbdiffusionsuebertragungsverfahren
US4478928A (en) * 1983-05-11 1984-10-23 Eastman Kodak Company Application of activated arylhydrazides to silver halide photography
EP0124795A2 (de) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidemulsionen
US4504570A (en) * 1982-09-30 1985-03-12 Eastman Kodak Company Direct reversal emulsions and photographic elements useful in image transfer film units
US4560638A (en) * 1984-10-09 1985-12-24 Eastman Kodak Company Halftone imaging silver halide emulsions, photographic elements, and processes which employ novel arylhydrazides
EP0200216A2 (de) 1985-04-30 1986-11-05 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Material
EP0204530A2 (de) 1985-05-31 1986-12-10 Konica Corporation Verfahren zur Herstellung eines direkt positiven Farbbildes
EP0210660A2 (de) 1985-07-31 1987-02-04 Fuji Photo Film Co., Ltd. Verfahren zur Bildung eines Bildes
US4650746A (en) * 1978-09-22 1987-03-17 Eastman Kodak Company High contrast photographic emulsions and elements and processes for their development
EP0217310A2 (de) * 1985-09-26 1987-04-08 International Paper Company Verbindungen und Zusammensetzungen nützlich als punktbefördernde Agenzien
EP0224214A2 (de) 1985-11-21 1987-06-03 Fuji Photo Film Co., Ltd. Lichtempfindliche Mikrokapsel, die Silberhalogenid und eine polymerisierbare Verbindung enthält und lichtempfindliches Material, das diese gebraucht
EP0228084A2 (de) 1985-12-25 1987-07-08 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung eines Bildes
US4684604A (en) * 1986-04-24 1987-08-04 Eastman Kodak Company Oxidative release of photographically useful groups from hydrazide compounds
EP0318987A1 (de) 1987-12-02 1989-06-07 Fuji Photo Film Co., Ltd. Photographisches lichtempfindliches Direktpositiv-Material
US4879203A (en) * 1987-04-06 1989-11-07 Ciba-Geigy Ag Process for producing masked positive color images by the silver dye bleach process
US4997980A (en) * 1985-09-26 1991-03-05 Anitec Image Corporation Ethanedioic acid hydrazide compounds suitable for use in high contrast photographic emulsions
US5064751A (en) * 1986-07-23 1991-11-12 Fuji Photo Film Co., Ltd. Method of processing a silver halide color photographic material and a color developer where the developer contains a hydrazine compound
US5187282A (en) * 1991-04-08 1993-02-16 Polaroid Corporation Sulfonated xanthene dyes, and photographic products and processes employing these dyes
EP0531014A2 (de) * 1991-09-03 1993-03-10 Minnesota Mining And Manufacturing Company Schwarz-weiss Film für graphische Kunst empfindlich für Multiwellenlängenbereiche
US5212045A (en) * 1990-05-09 1993-05-18 Mitsubishi Paper Mills Limited Method for image formation
US5264322A (en) * 1991-04-08 1993-11-23 Polaroid Corporation Sulfonated xanthene dyes, and photographic products and processes employing these dyes
EP0782041A2 (de) 1995-12-27 1997-07-02 Fuji Photo Film Co., Ltd. Lichtempfindliches photographisches Silberhalogenid-Material
EP0782042A2 (de) 1995-12-27 1997-07-02 Fuji Photo Film Co., Ltd. Hydrazin-Verbindung und diese enthaltendes photographisches Silberhalogenidmaterial
US5871880A (en) * 1995-11-30 1999-02-16 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material and image-forming method
US5976756A (en) * 1995-11-30 1999-11-02 Fuji Photo Film, Co., Ltd. Color diffusion transfer silver halide photographic materials and process for forming images
US6380288B1 (en) * 1997-04-02 2002-04-30 Bridgestone Corporation Rubber composition and pneumatic tires

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE570272A (de) * 1956-03-07
US2309492A (en) * 1939-07-14 1943-01-26 Gen Aniline & Film Corp Process for avoiding color fog on photographic color material
US2563785A (en) * 1950-04-29 1951-08-07 Eastman Kodak Co Direct positive photographs from hydrazine-containing developers
US2588982A (en) * 1950-10-26 1952-03-11 Eastman Kodak Co Direct positive photographs using hydrazine in the emulsion
US2701197A (en) * 1951-12-15 1955-02-01 Eastman Kodak Co Nonpolymeric sulfonated hydroquinone antistain agents
US2756142A (en) * 1953-01-22 1956-07-24 Eastman Kodak Co Photographic color reproduction process
US2930694A (en) * 1956-03-19 1960-03-29 Agfa Ag Optical sensitization of direct positive emulsions
US2940849A (en) * 1957-07-10 1960-06-14 Eastman Kodak Co Planographic dye transfer process

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2309492A (en) * 1939-07-14 1943-01-26 Gen Aniline & Film Corp Process for avoiding color fog on photographic color material
US2563785A (en) * 1950-04-29 1951-08-07 Eastman Kodak Co Direct positive photographs from hydrazine-containing developers
US2588982A (en) * 1950-10-26 1952-03-11 Eastman Kodak Co Direct positive photographs using hydrazine in the emulsion
US2701197A (en) * 1951-12-15 1955-02-01 Eastman Kodak Co Nonpolymeric sulfonated hydroquinone antistain agents
US2756142A (en) * 1953-01-22 1956-07-24 Eastman Kodak Co Photographic color reproduction process
BE570272A (de) * 1956-03-07
US2930694A (en) * 1956-03-19 1960-03-29 Agfa Ag Optical sensitization of direct positive emulsions
US2940849A (en) * 1957-07-10 1960-06-14 Eastman Kodak Co Planographic dye transfer process

Cited By (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3351465A (en) * 1962-12-28 1967-11-07 Polaroid Corp Photographic diffusion transfer processes utilizing a processing composition containing potassium and lithium ions
US3330655A (en) * 1963-09-20 1967-07-11 Eastman Kodak Co Preparation of photographic direct positive color images
US3352672A (en) * 1964-04-09 1967-11-14 Eastman Kodak Co Photographic direct positive color process and element
US3620747A (en) * 1968-05-20 1971-11-16 Eastman Kodak Co Photographic element including superimposed silver halide layers of different speeds
USRE28760E (en) * 1968-05-20 1976-04-06 Eastman Kodak Company Photographic element including superimposed silver halide layers of different speeds
DE2020814A1 (de) * 1969-04-28 1970-11-12 Eastman Kodak Co Photographisches Aufzeichnungsmaterial
FR2128801A1 (de) * 1971-03-11 1972-10-20 Eastman Kodak Co
US3793027A (en) * 1971-03-26 1974-02-19 Fuji Photo Film Co Ltd Developing composition for use with photographic materials for the graphic arts
US3942987A (en) * 1973-02-12 1976-03-09 Eastman Kodak Company Photographic materials with ballasted, alkali cleavable azo dyes
US3984245A (en) * 1973-10-09 1976-10-05 Fuji Photo Film Co., Ltd. Photographic sensitive materials
US4268606A (en) * 1974-02-05 1981-05-19 Eastman Kodak Company Azo dye compounds and photographic materials
US3954476A (en) * 1974-02-05 1976-05-04 Eastman Kodak Company Diffusable dye-releasing compounds which are cleavable upon oxidation
US4141730A (en) * 1975-04-08 1979-02-27 Fuji Photo Film Co., Ltd. Multilayer color photographic materials
US4031127A (en) * 1975-08-06 1977-06-21 Eastman Kodak Company Acyl hydrazino thiourea derivatives as photographic nucleating agents
US4030925A (en) * 1975-08-06 1977-06-21 Eastman Kodak Company Photographic compositions and elements including internal latent image silver halide grains and acylhydrazinophenylthiourea nucleating agents therefor
US4030920A (en) * 1976-04-12 1977-06-21 Eastman Kodak Company Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement
US4080207A (en) * 1976-06-29 1978-03-21 Eastman Kodak Company Radiation-sensitive compositions and photographic elements containing N-(acylhydrazinophenyl) thioamide nucleating agents
US4166742A (en) * 1976-10-18 1979-09-04 Fuji Photo Film Co., Ltd. Contrasty light-sensitive silver halide material containing a hydrazine derivative and a heterocyclic mercaptan
JPS5384714A (en) * 1976-12-30 1978-07-26 Fuji Photo Film Co Ltd High sensitivity and high contrast photographic material
JPS5814664B2 (ja) * 1976-12-30 1983-03-22 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の処理方法
US4377634A (en) * 1977-09-06 1983-03-22 Fuji Photo Film Co., Ltd. Method for forming high contrast photographic image
US4139387A (en) * 1977-10-19 1979-02-13 Agfa-Gevaert Aktiengesellschaft Process for the production of direct-positive photographic images
US4266013A (en) * 1977-11-28 1981-05-05 Fuji Photo Film Co., Ltd. Direct positive silver halide light-sensitive material and method of forming direct positive image
US4386149A (en) * 1978-02-28 1983-05-31 Ciba-Geigy Ag Process for the production of photographic images by dye diffusion transfer and photographic material suitable in this process
US4268621A (en) * 1978-07-29 1981-05-19 Konishiroku Photo Industry Co., Ltd. Direct positive photographic material
US4650746A (en) * 1978-09-22 1987-03-17 Eastman Kodak Company High contrast photographic emulsions and elements and processes for their development
US4279987A (en) * 1978-11-14 1981-07-21 Konishiroku Photo Industry Co., Ltd. Light-sensitive, direct positive silver halide photographic material
US4306016A (en) * 1980-10-16 1981-12-15 Eastman Kodak Company Photographic emulsions and elements capable of forming direct-positive images
US4315986A (en) * 1980-11-10 1982-02-16 Eastman Kodak Company Photographic emulsions and elements capable of forming direct-positive images
US4306017A (en) * 1980-11-17 1981-12-15 Eastman Kodak Company Photographic emulsions and elements capable of forming direct-positive images
US4374923A (en) * 1980-11-19 1983-02-22 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic light-sensitive material
JPS57150845A (en) * 1981-03-13 1982-09-17 Fuji Photo Film Co Ltd Silver halide photographic material
JPS6323533B2 (de) * 1981-03-13 1988-05-17 Fuji Photo Film Co Ltd
US4504570A (en) * 1982-09-30 1985-03-12 Eastman Kodak Company Direct reversal emulsions and photographic elements useful in image transfer film units
DE3413049A1 (de) * 1983-04-07 1984-10-11 Fuji Photo Film Co., Ltd., Minamiashigara, Kanagawa Photographisches element fuer farbdiffusionsuebertragungsverfahren
US4533622A (en) * 1983-04-07 1985-08-06 Fuji Photo Film Co., Ltd. Photographic element for color diffusion transfer process containing hydroquinone sulfonates
EP0124795A2 (de) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidemulsionen
US4478928A (en) * 1983-05-11 1984-10-23 Eastman Kodak Company Application of activated arylhydrazides to silver halide photography
US4459347A (en) * 1983-05-11 1984-07-10 Eastman Kodak Company Adsorbable arylhydrazides and applications thereof to silver halide photography
US4560638A (en) * 1984-10-09 1985-12-24 Eastman Kodak Company Halftone imaging silver halide emulsions, photographic elements, and processes which employ novel arylhydrazides
EP0200216A2 (de) 1985-04-30 1986-11-05 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Material
EP0204530A2 (de) 1985-05-31 1986-12-10 Konica Corporation Verfahren zur Herstellung eines direkt positiven Farbbildes
EP0210660A2 (de) 1985-07-31 1987-02-04 Fuji Photo Film Co., Ltd. Verfahren zur Bildung eines Bildes
EP0217310A2 (de) * 1985-09-26 1987-04-08 International Paper Company Verbindungen und Zusammensetzungen nützlich als punktbefördernde Agenzien
US4997980A (en) * 1985-09-26 1991-03-05 Anitec Image Corporation Ethanedioic acid hydrazide compounds suitable for use in high contrast photographic emulsions
US4686167A (en) * 1985-09-26 1987-08-11 Anitec Image Corporation Compositions comprising ethane dioic acid hydrazide compounds and derivatives useful as dot-promoting agents
EP0217310A3 (en) * 1985-09-26 1989-02-01 Anitec Image Corporation Compounds and composition useful as dot promoting agents
EP0224214A2 (de) 1985-11-21 1987-06-03 Fuji Photo Film Co., Ltd. Lichtempfindliche Mikrokapsel, die Silberhalogenid und eine polymerisierbare Verbindung enthält und lichtempfindliches Material, das diese gebraucht
EP0228084A2 (de) 1985-12-25 1987-07-08 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung eines Bildes
US4684604A (en) * 1986-04-24 1987-08-04 Eastman Kodak Company Oxidative release of photographically useful groups from hydrazide compounds
US5064751A (en) * 1986-07-23 1991-11-12 Fuji Photo Film Co., Ltd. Method of processing a silver halide color photographic material and a color developer where the developer contains a hydrazine compound
US4879203A (en) * 1987-04-06 1989-11-07 Ciba-Geigy Ag Process for producing masked positive color images by the silver dye bleach process
EP0318987A1 (de) 1987-12-02 1989-06-07 Fuji Photo Film Co., Ltd. Photographisches lichtempfindliches Direktpositiv-Material
US5212045A (en) * 1990-05-09 1993-05-18 Mitsubishi Paper Mills Limited Method for image formation
US5187282A (en) * 1991-04-08 1993-02-16 Polaroid Corporation Sulfonated xanthene dyes, and photographic products and processes employing these dyes
US5264322A (en) * 1991-04-08 1993-11-23 Polaroid Corporation Sulfonated xanthene dyes, and photographic products and processes employing these dyes
EP0531014A2 (de) * 1991-09-03 1993-03-10 Minnesota Mining And Manufacturing Company Schwarz-weiss Film für graphische Kunst empfindlich für Multiwellenlängenbereiche
EP0531014A3 (en) * 1991-09-03 1993-03-24 Minnesota Mining And Manufacturing Company Multi-wavelength sensitive black-and-white graphic arts film
US5871880A (en) * 1995-11-30 1999-02-16 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material and image-forming method
US5976756A (en) * 1995-11-30 1999-11-02 Fuji Photo Film, Co., Ltd. Color diffusion transfer silver halide photographic materials and process for forming images
EP0782041A2 (de) 1995-12-27 1997-07-02 Fuji Photo Film Co., Ltd. Lichtempfindliches photographisches Silberhalogenid-Material
EP0782042A2 (de) 1995-12-27 1997-07-02 Fuji Photo Film Co., Ltd. Hydrazin-Verbindung und diese enthaltendes photographisches Silberhalogenidmaterial
US6380288B1 (en) * 1997-04-02 2002-04-30 Bridgestone Corporation Rubber composition and pneumatic tires

Also Published As

Publication number Publication date
BE636671A (de)
BE603747A (de)
DE1167655B (de) 1964-04-09
GB1061294A (en) 1967-03-08

Similar Documents

Publication Publication Date Title
US3227552A (en) Preparation of photographic direct positive color images
US3364022A (en) Direct positive photographic color reproduction process and element utilizing thio-substituted hydroquinones as development inhibitors
US3227551A (en) Photographic color reproduction process and element
US3342599A (en) Schiff base developing agent precursors
US3765891A (en) Process for developing photographic elements
US3227550A (en) Photographic color reproduction process and element
JP2656924B2 (ja) 写真要素
US3458315A (en) Cyan couplers for color photography
US3582322A (en) Color photographic elements and process
US4208210A (en) Process for forming an optical soundtrack
EP0056444B1 (de) Photographische Elemente, die blockierte photographische Reagenzien enthalten, und Verfahren, in denen diese verwendet werden
US3862842A (en) Image-forming processes and compositions
US3243294A (en) Photographic direct-positive color process
US4358532A (en) Photographic element
US3698896A (en) Diffusion transfer film unit with improved dye image receiving layer comprising a basic polymeric mordant
US3689272A (en) Photographic color processes which yield either positive or negative silver-transfer images
US3415652A (en) Silver halide color photographic elements utilizing alpha-sulfonyloxy substituted two-equivalent yellow-forming couplers
US3352672A (en) Photographic direct positive color process and element
US3923511A (en) Photographic process and composition employing CO(III) complexes and silver halide solvents
US3547640A (en) Multicolor photographic elements
US3960569A (en) Diffusion transfer color film unit with hydroxy substituted alkylene amino development accelerators
US4069048A (en) Diffusion transfer photographic materials with color developer scavenger
US3846130A (en) Process for developing photographic elements
US3846128A (en) Photosensitive elements having improved processing temperature latitude
US3834907A (en) Photographic elements containing color-providing layer units for amplification processes