US3719492A

US3719492A - Complexed p-phenylenediamine containing photographic element and development process therefor

Info

Publication number: US3719492A
Application number: US00121590A
Authority: US
Inventors: C Barr; M Pfaff
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1971-03-05
Filing date: 1971-03-05
Publication date: 1973-03-06
Anticipated expiration: 1990-03-06

Abstract

COLOR PHOTOGRAPHIC ELEMENTS COMPRISING A SUPPORT COATED WITH AT LEAST ONE HYDROPHILIC COLLOID LAYER CONTAINING LIGHT-SENSITIVE SILVER HALIDE AND A NONDIFFUSIBLE COUPLER THAT REACTS WITH OXIDIZED AROMATIC PRIMARY AMINE COLOR DEVELOPING AGENT TO FORM A NONDIFFUSIBLE DYE AND COATED ON THE SAME SIDE OF THE SUPPORT AT LEAST ONE HYDROPHILIC COLLOID LAYER CONTAINING A PHOTOGRAPHICALLY COMPATIBLE, INACTIVE COLOR DEVELOPING AGENT PRECURSOR FORMED BY REACTING (1) A WATER-SOLUBLE POLYVALENT METAL SALT WITH (2) A WATER-SOLUBLE AND DIFFUSIBLE P-PHENYLENEDIAMINE COLOR DEVELOPING AGENT OR ACID SALT THEREOF. THE IMMEDIATE ELEMENTS HAVE GOOD STABILITY WITH SUBSTANTIALLY NO CHANGE PRODUCED BY TTHE COLOR DEVELOPING AGENT PRECURSOR DURING STORAGE AND ARE ADVANTAGEOUSLY COLOR DEVELOPED BY CONTACTING THE PHOTOGRAPHIC ELEMENT WITH AN AQUEOUS ALKALINE ACTIVATOR SOLUTION WHICH RAPIDLY RELEASES ACTIVE COLOR DEVELOPING AGENT FROM THE PRECURSOR.

Description

United States Patent Int. Cl. G03c 7/00 U.S. Cl. 96-55 24 Claims ABSTRACT OF THE DISCLOSURE Color photographic elements comprising a support coated with at least one hydrophilic colloid layer containing light-sensitive silver halide and a nondiffusible coupler that reacts with oxidized aromatic primary amine color developing agent to form a nondiffusible dye and coated on the same side of the support at least one hydrophilic colloid layer containinga photographically compatible, inactive color developing agent precursor formed by reacting (1) a Water-soluble polyvalent metal salt with (2) a Water-soluble and ditfusible p-phenylenediamine color developing agent or acid salt thereof. The immediate elements have good stability with substantially no change produced by the color developing agent precursor during storage and are advantageously color developed by contacting the photographic element with an aqueous alkaline activator solution which rapidly releases active color developing agent from the precursor.

This invention relates to light-sensitive photographic silver halide elements, more particularly to photographic silver halide elements which contain a photographically compatible precursor of a color developing agent.

In the preparation of silver halide emulsions for recording colors, it is customary to incorporate a color-forming material in the silver halide emulsion so that upon color development, this color-forming compound (coupler) reacts with the oxidation product of the developing agent to form a dye. In the typical emulsion for recording within the visible spectrum, the emulsion is coated in several layers, each sensitive to a particular region of the spectrum. By suitable control of the development and by use of appropriate couplers,,it is possible to form the proper dye in each layer to give an adequate color representation of the light image-producing the original exposure. Subsequently, the silver image formed during the color development step and residual silver halide in the photographic element are removed by bleaching and then fixing or, alternatively, by a combined bleach-fix bath leaving the dye image reproduction in the photographic element.

A p-phenylenediamine color developing agent is most commonly used for the color development of color photographic elements. The p-phenylenediamines are used in color developing baths since it has not been feasible to incorporate these developers in a silver halide emulsion or in another hydrophilic colloid layer of the photographic element adjacent to the silver halide emulsion layer. The incorporation of color developing agents in photographic emulsions generally gives rise to basic problems such as desensitization, increased fog and/or speed loss during storage of photographic material. Accordingly, it has been desirable to find a means of incorporating a p-phenylenediamine developer or precursor thereof in the photographic element and, at the same time, to provide a stable photographic element which can be stored without change in photographic quality.

Barr U.S. Pat. 3,295,978 describes the incorporation of metal salts of black-and-white developers, such as catechol and hydroquinone in photographic silver halide emulsion ice layers. After image exposure, these photographic elements are developed by treating the element with an activator solution containing an anion, such as sulfate, sulfite, thiocyanate, chloride, bromide, iodide, etc., which is capable of forming a less dissociated compound than the precursor with the metal ions from the precursor at a pH high enough to activate the developing agent freed from the precursor, usually pHs of about 11 cause image development. The exact structure of the metal salts of these developers used as developing agent precursors is not known with certainty.

Harnish et al., U.S. Pat. 3,342,597 describes the use of indoaniline dyes as developing agent precursors in photographic elements.

Other photographic elements are desired which contain other precursors of color developing agents, preferably precursors which have little, if any, color, which do not cause any stability problems on storage and which are rapidly activated by an activator solution during the development step.

It is, therefore, an object of our invention to provide a novel color photographic element containing a photographically compatible precursor of a p-phenylenediamine color developing agent which has good stability during storage and does not show desensitization, increased fog and/ or speed loss during storage.

Another object of our invention is to provide a novel photographic color element containing photographically compatible color-developing agent precursors which not only have good stability on storage, but which release the active color developer at a rapid rate when treated with an activator bath during photographic processing.

Another object of our invention is to provide a novel process for forming a dye image in a photographic silver halide element containing a precursor of a color developing agent by simply contacting the image-exposed element with an aqueous alkaline activator solution.

Still further objects of our invention will become evident from the consideration of the following specification and claims.

These and still other objects of our invention are accomplished according to our invention by preparing and using our color photographic element comprising a support having coated thereon at least one hydrophilic colloid layer containing silver halide and on the same side of the support at least one hydrophilic colloid layer containing at least one of our photographically compatible color developing agent precursors that is the reaction product of (1) a water-soluble salt of a polyvalent metal and (2) a water-soluble and diifusible p-phenylenediamine color developing agent. Our novel photographic elements have good stability upon storage, but rapidly release active p-phenylenediamine color developing agent when treated with aqueous alkaline solution. By a photographically compatible developing agent precursor, we mean any such precursor which, when incorporated into or contiguous to a lightsensitive silver halide emulsion, does not adversely affect the sensitometric properties of the silver halide emulsion such as speed, fog, contrast and the like.

The water-soluble salts of polyvalent metals, preferably divalent metals, used in preparing the developer precursors used in this invention, include those represented by the formula:

wherein M+ represents a polyvalent metal, such as, cadmium, copper, lead, zinc, etc.; q represents an integer of 2 or 3, the valence of the metal; r represents an integer of 1 or 2; X represents an acid anion, such as, chloride,

The water-soluble and ditfusible p-phenylenediamine color developing agents used to advantage in the developer precursors used in the invention include those having the formula:

cupric nitrate cupric sulfate lead chloride lead chlorate lead acetate zinc chloride zinc bromide zinc iodide zinc chlorate zinc nitrate zinc sulfate zinc acetate IFIHa a R (HEX- T wherein R, R R and R are the same or diiferent and include hydrogen, an alkyl group of from 1 to 5 carbon atoms, such as, alkyl (e.g., methyl, ethyl, propyl, butyl, amyl, etc.), substituted alkyl, such as, hydroxy alkyl (e.g., hydroxymethyl, hydroxybutyl, etc.), a haloalkyl group (e.g., chlorocthyl, bromoethyl, etc.), a sulfoalkyl group (e.g., sulfoethyl, sulfopropyl, sulfobutyl, etc.), a carboxyalkyl group (e.g., carboxymethyl, carboxyethyl, carboxybutyl, etc.), an alkylsulfonamido alkyl group (e.g., methylsulfonamidomethyl, ethylsulfonamidomethyl, etc.), an alkoxy group having from 1 to 5 carbon atoms (c.g., methoxy, ethoxy, propoxy, amyloxy, etc.); or acetamido; X- represents an anion, such as, chloride, bromide, iodide, acetate, nitrate, chlorate, bromate, sulfate, etc.; m represents an integer of from '1 to '2, the valence of X; and n represents an integer of from 1 to 3.

Photographically compatible inactive color developing agent precursors useful in the invention include those represented by the formula:

(III) NH:

Dichloro-p-pheny1enediamine cadmium II or as the dimer tetrachloro-a-dl-(p-phenylenediamine)di-cadmium (II) Dich10ro-p-phenylenediamine zinc (II) or as the dimer tetrachloro-c-di-(p-phenylenediamine)dizrnc (II) Dichloro-p-phenylenediamine copper (II) or as the dimer tetrachloro-a-dip-phenylenediamine dicopper (II) Dichloro-p-phenylenediamine lead (II) or as the dimer tetrachloro-a-di-(p-phenylenediamine)dilead (II) Dinitrate-p-phenylenediamine cadmium (II) or as the dimer tetranitrate-n-dip-phenylenediamine) dicadmium (II) Sulfatodiaquo-p-phenylenediamine cadmium (II) or as the dimer Id)isulfatotetraaquo-nflb p-phenylenediamine) dicadmium Diacetoxy-p-phenylenediamine cadmium (II) or as the dimer tetraacetoxy-a-di- (p-phenylenediamine) dicadmium (II) Dibromato-p-phenylenediamine cadmium (II) or as the dimer tetrabromato-u-di- (p-phenylenediamine) dicadmium (II) Dibromop-phenylenediamine cadmium (II) or as the dimer tetrabrom0u-di- (p-phenylenediamine) dicadmium (II) [P* 6 4 a z] CdCLf D- nylenediaminium tetrachlorocadmiumate (II) ITIH:

CHa

[CdCsl'HzO 1- (N,N-diethy1) -3-methyi-4-pheny1enediaminium trichloroaquocadmiumate (II) 1' (N-ethyl-N-fl-hydroxyethyl -3-methyl-4 plienylenediaminium dichlorosulfatocadmiumate (II) 1- (N,N-diethyl -3-H-methanesulfonamidoethyl-4-phenylenediaminium tetrachlorocadmiumate (II) These and other color developing agent precursors formed by the reaction of (1) a water-soluble polyvalent metal salt with (2) a water-soluble and dilfusible aromatic primary amine color developing agent, preferably a pphenylenediamine color developing agent, are used to advantage in the invention, including precursors having Formula III.

In general, such developing agent precursors are prepared by mixing an aqueous solution of a water-soluble salt of a polyvalent metal having the formula: MX defined previously, into an aqueous solution of a watersoluble and diffusible p-phenylenediamine color developing agent or acid salt thereof and causing the precursor to precipitate. It is advantageous to use in the range of from equimolar amounts of the reactants to a 400% excess of the salt of the polyvalent metal. It is advantageous to precipitate the precursors derived from an acid salt of the color developing agent by cooling the reaction mixture. The precursor is then advantageously purified if desired to remove excess reactants. The purified precursor derived from the acid salt of the color developing agent is water-soluble and is advantageously added to the hydrophilic colloid coating composition in solution. Since our precursors derived from the color developing agent per se (i.e., not the acid salt of the developing agent) are not soluble in water, it is advantageous to precipitate them in the presence of hydrophilic colloid to prevent particles of the precipitating precursor from becoming larger than is desired. The gelatin solution containing the precipitated develo ing agent precursor is advantageously chilled, noodled and washed it it is desired to remove excess reactants.

The preparation of Precursor No. 1 is described in Example 1. Precursors 2 through 9 are advantageously prepared in a manner similar to that described for Precursor No. 1, but using the appropriate reactants. The preparation of Precursor No. 10 is described in Example 3. Precursors 11 through 14 are prepared in a manner similar to Precursor 10, but by using the appropriate reactants.

Such precursors of color developing agents are advantageously prepared from any of the p-phenylenediamine color developing agents known in the art since they have the pair of electrons needed for complex formation. Some specific types of color developing agents used to advantage are disclosed in the Journal American Chemical Society, 73, 3100 (1951), R. L. Bent et al.

Our precursors of p-phenylenediamine color developing agents are advantageously coated in the light-sensitive silver halide hydrophilic colloid layer(s) and/or in another hydrophilic colloid layer on the same side of the support (for the photographic element), preferably contiguous to the light-sensitive layer. It is particularly advantageous to incorporate the developing agent precursors in a layer between the support and the light-sensitive layer closest to the support, although many of the precursors have very little, if any, color and are incorporated in the light-sensitive layers. The cupric chloride complex of p-phenylenediamine is black in color and the layer containing it advantageously serves as a bleachable antihalation layer between the support and the first lightsensitive layer as well as a source of active color developing agent upon activation during processing.

The color developing agent precursors used in the invention are advantageously coated in hydrophilic colloid layers of our photographic elements over a wide range of coating rates, preferably so that there is a mole ratio of precursor to silver halide of at least about 1:1.

Our photographic elements are advantageously coated on any of the typical photographic supports including cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthalate) film, polyethylene film, polypropylene film and related films of resinous materials, as well as paper, glass and others.

Our photographic elements comprise a support with at least one hydrophilic colloid layer containing silver halide and a nondifiusible color-forming coupler that reacts with oxidized aromatic primary amine color developing agent to form a nondiftusible dye and on the same side of the support at least one hydrophilic colloid layer that contains at least one of our precursors of a p-phenylenediamine color developing agent. Usually our photographic elements are multicolor and contain two or more emulsion layers sensitive to difierent regions of the actinic spectrum. In one of our elements, the support is coated in succession with a layer containing our color developing agent precursor, a red-sensitized silver halide emulsion layer containing a nondiffusible phenolic or nondiffusible naphthoic cyan-dye forming coupler, a greensensitized silver halide emulsion layer containing a nondiffusible magenta-dye-forrning coupler, such as, a 5- pyrazolone coupler, a blue sensitive silver halide emulsion layer containing a nonditfusible open-chain yellowdye-forming coupler, either with or without a bleachable blue light-absorbing filter layer between the green-sensitive and blue-sensitive layers, other interlayers, antihalation layer, overcoat layer, etc. The couplers and differently sensitized layers are also arranged on one or both sides of the support in the same or other orders.

In photographic elements where there are light-sensitive layers on both sides of a transparent support, it is advantageous to have a hydrophilic colloid layer on both sides of the support containing at least one of our color developing agent precursors. The differently sensitized layers are advantageously double-coated as described in German Pat. 1,121,470, Wolf et al. US. Pat. 3,516,831, etc.

Hydrophilic colloid used to advantage in the silver halide emulsion or for separate layers containing the feature developing agent precursor include gelatin, colloidal albumin, a cellulose derivative or a synthetic resin, for instance, a polyvinyl compound. Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe US. Pat. 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19- 26% as described in Lowe et al. U.S. Pat. 2,327,808, issued Aug. 24, 1943; a water-soluble ethanolamine cellulose acetate as described in Yutzy US. 2,322,085, issued June 15, 1943; a polyacrylamide having a combined acrylamide content of 30-60% and a specific viscosity of 0.25- 1.5 and an imidized polyacrylamide of like acrylamide content and viscosity as described in Lowe et 'al. US. Pat. 2,541,474, issued Feb. 13, 1951; zein as described in Lowe US. Pat. 2,563,791, issued Aug. 7, 1951, a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in Unruh et al. US. Pat. 2,768,154, issued Oct. 23, 1956, or containing cyano-acetyl groups, such as the vinyl alcohol-vinyl cyano-acetate copolymer as described in Unruh et al. US. Pat. 2,808,331, issued Oct. 1, 1957; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in Illingsworth et al. US. Pat. 2,852,382, issued Sept. 16, 1958. Polyvinyl pyrolidone and mixtures of it with the other hydrophilic colloids described above are also advantageously used.

Any of the photographic silver halide emulsions, e.g., silver bromide, silver bromoiodide, silver chloride, silver chlorobromide, silver bromochloroiodide, etc., used in photography are used to advantage in our photographic materials. Negative developing-out silver halide emulsions, as well as reversal emulsions such as described in US. 2,592,250, can be used.

The emulsions used in the photographic elements of our invention are advantageously chemically sensitized by any of the accepted procedure. The emulsions can be digestcd with naturally active gelatin, or sulfur compounds can be added, such as those described in Sheppard US. Pat. 1,574,944, issued Mar. 2, 1926; Sheppard et al. US.

7 Pat. 1,623,499, issued Apr. 5, 1927; and Sheppard et al. U.S. Pat. 2,410,689, issued Nov. 5, 1946.

The emulsions are advantageously treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum, as described in Smith et a1. U.S. Pat. 2,448,060, issued Aug. 31, 1948 and as described in Trivelli et al. U.S. Pats. 2,566,245 and 2,566,263, both issued Aug. 28, 1951.

The emulsions are advantageously sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Pats. 1,846,301 and 1,846,302, both issued Feb. 23, 1932; and 1,942,854, issued Ian. 9, 1934; White U.S. Pat. 1,990,507, issued Feb. 12, 1935; Brooker and White U.S. Pats. 2,122,140, issued Mar. 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued Ian. 10, 1950; and 2,739,964, issued Mar. 27, 1956; Brooker et al. U.S. Pat. 2,493,748, issued Jan. 10, 1950; Sprague U.S. Pats. 2,503,776, issued Apr. 11, 1950 and 2,519,001, issued Aug. 15, 1950; Heseltine et al. U.S. Pat. 2,666,761, issued Jan. 19, 1954; Heseltine U.S. Pat. 2,734,900, issued Feb. 14, 1956; VanLare U.S. Pat. 2,739,149, issued Mar. 20, 1956; and Kodak Limited British 450,958, accepted July 15, 1936.

The emulsions also advantageously contain speedincreasing compounds of the quaternary ammonium type of Carroll US. Pat. 2,271,623, issued Feb. 3, 1942; Carroll et al. U.S. Pat. 2,288,226, issued June 30, 1942; and Carroll et al. U.S. Pat. 2,334,864, issued Nov. 23, 1943; and the polyethylene glycol type of Carroll et al. U.S. Pat. 2,708,162, issued May 10, 1955.

The emulsions are also advantageously chemically sensitized with gold solts as described in Waller et al. U.S. Pat. 2,399,083, issued Apr. 23, 1946, or stabilized with gold salts as described in Damschroder U.S. Pat. 2,597,856, issued May 27, 1952; and Yutzy et a1. U.S. Pat. 2,597,915, issued May 27, 1952. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazole methochloride.

In addition to the addenda already described, our emulsions also advantageously contain any of the wellknown stabilizers; antifoggants; speed-increasing materials, such as polyalkylene oxides, onium salts and thioethers; plasticizers; coating aids, such as anionic, nonionic and amphoteric surface active compounds and the like. In addition to the chemical sensitization of our hydrophilic colloid silver halide emulsions described above, our emulsions are also advantageously reduction sensitized with reducing agents.

The various layers of the photographic elements of our invention are advantageously hardened with any of the known hardeners including, for example, aldehyde hardeners, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides, such as oxystarch, oxyplant gums and the like.

Usually the couplers are used to advantage in our materials and are ballasted to make them nondifiusible in the silver halide emulsions in which they are incorporated. The couplers utilized in our invention can be dispersed in a high-boiling, crystalloidal compound which can be used as a vehicle for incorporating the coupler in the photographic emulsion according to methods well known in the art. Various other known methods of incorporating the color-forming couplers in our element may also be utilized. For example, the low solvent dispersion described in Fierke U.S. Pat. 2,801,107 is used to advantage; or the couplers may be dispersed in natural resin-type solvents as described in Martinez U.S. Pat. 2,284,879; or the couplers may be dissolved in monomeric solution which is then polymerized in the presence of gelatin to produce dispersions of the coupler in the polymer as described in U.S. Pat. 2,825,382. Alternatively, the 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.

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

EXAMPLE 1 The cadmium chloride complex of p-phenylenediamine is prepared as follows: 10.8 g. of p-phenylenediamine dissolved in 150 ml. of water is mixed into g. of a 20% bone gelatin solution, then 38.5 g. of cadmium chloride in ml. of water is added to the mixture with strong stirring and the combined mixture adjusted to 500 g. with water. Into 70 g. of a gelatino silver chloride emulsion, having a weight of 7 kg. per gallon, is dispersed 100 g. of a solution of the cyan-forming coupler, l-hydroxy-N- [6-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide, in tricresylphosphate, 50 g. of the cadmium chloride complex of p-phenylenediamine in gelatin, then 100 ml. of water, 10 cc. of 15% Saponin and 10 ml. of a 2.16% chrome alum solution in water is added and the resulting coating composition intimately blended. A paper support is coated with the coating composition at a wet coverage of g./m. to give a silver coverage of about 8 mg. of silver/ dm. This coating is dried, and exposed to a light image to form a latent image in the silver halide. Treatment of the exposed photographic paper for 2 minutes at 20 C. in a solution of 50 g. of sodium carbonate per liter of water gives a cyan dye image and a silver image reproduction of the light image used in the exposure. The silver image is removed by treating the developed image with a conventional bleach comprising an aqueous solution of potassium ferricyanide, followed by treating the bleached element in a conventional aqueous fixing bath comprising sodium thiosulfate, leaving a cyan dye image reproduction of the light image used in the exposure.

EXAMPLE 2 A piece of the exposed, but unprocessed, photographic paper made in Example 1 is placed in a heat-seal wrapper and incubated for 5 days at 50 C. A second piece of the exposed, but unprocessed, photographic paper is held at room temperatures for 5 days as a control. The incubated paper and the control are then processed as described in Example 1 to produce cyan dye image reproductions of the light image used to make the exposures. The results show the cyan dye image reproduction in the incubated paper is substantially the same as the cyan dye image in the control.

EXAMPLE 3 The cadmium chloride complex of p-phenylenediamine di-hydrogen chloride is prepared as follows: 18.1 g. of p-phenylenediamine di-hydrogen chloride is dissolved in 200 ml. of distilled water at 40 C. This solution is treated with a solution of 18.3 g. of cadmium chloride dissolved in 25 ml. of distilled water. The mixture is heated for 5 minutes and then cooled to 5 C. to complete the precipitation. The solid complex is filtered, washed in ethanol and diethylether, and air dried. The cadmium chloride complex of p-phenylenediamine di-hydrogen chloride is coated on a cellulose acetate film support from a gelatin solution at 3777 mg. of the complex/m2, i.e., in a 1:1 molar ratio to silver. A red-sensitive sulfur and goldsensitized gelatino silver bromoiodide emulsion containing a dispersion of cyan-dye-forrning naphthol coupler of the type described in Weissberger et al., U.S. Pat. 2,474,293, is coated over the developer complex layer at 1111 mg. silver and 3022 mg. gelatin per m. One sample of the coating is light exposed overall and another sample is light exposed to a step tablet test pattern, then activated in a 0.1 N sodium hydroxide solution containing a small amount of sodium bromide to decrease background fog, bleached in a conventional potassium ferricyanide bleach, fixed in a conventional fixing bath containing sodium thiosulfate, washed and dried. The resulting coatings contain a cyan dye image corresponding to the light exposure given them before photographic proc- 9 essing. Density readings made on a densitometer using a red coated filter show a cyan dye D of 1.45 density units in the overall exposed sample and a cyan dye D of 0.53 and a D of 0.08 density unit in the sample exposed to light through the step tablet.

EXAMPLE 4 Three photographic elements are made by coating on a cellulose acetate film support a gelatin solution containing the addendum indicated in the table below, and over this layer is coated the red-sensitive sulfur and goldsensitized gelatino silver bromoiodide emulsion containing the dispersion of cyan-dye-forming coupler as described in Example 3. A sample of each of the three photographic elements is exposed for /25 second to a step tablet on a sensitometer and processed by pressing them into contact with a gelatin pad which had been imbibed for 60 seconds in an activator bath comprising an aqueous solution of 1% by weight potassium hydroxide plus by weight of sodium sulfate. After three minutes, the photographic elements are separated from the gelatin pad, placed in an acid stop bath and then a conventional sodium thiosulfate fixing bath. The D and D values are listed in the table below.

TABLE Addenda (gJAg mole) cadmium chloride com- Photographic plex of p-phenyleneresults Element diamine dihydrogen No. chloride Dmin Drunx EXAMPLE 5 Examples 1 and 2 are repeated but using in place of the cyan coupler a nondiffusible magenta-forming 5- pyrazolone coupler of the type described in Loria et al. US. Pat. 2,600,788. A magenta dye image reproduction is produced. The magenta dye image in the incubated photographic paper is substantially the same as the magenta image in the control.

EXAMPLE 6 Examples 1 and 2 are repeated but using in place of the cyan coupler a nondiffusible yellow-dye-forming coupler of the type described in McCrossen et al. US. Pat. 2,875,057. A yellow dye image reproduction is produced. The yellow dye image in the incubated photographic paper is substantially the same as the yellow image in the control.

EXAMPLE 7 Examples 1 and 2 are repeated but instead of using the cadmium chloride complex of p-phenylenediamine (i.e., dichloro-p-phenylenediarnine cadmium II), an equivalent amount of dichloro-p-phenylenediamine zinc (II) is used. This is formed by substituting an equimolar amount of zinc chloride for cadmium chloride. Photographic results are obtained that are similar to those obtained in Examples 1 and 2.

EXAMPLE 8 1 and 2.

EXAMPLE 9 Example 8 is repeated but in place of dichloro-pphenylenediamine cadmium (II), an equwalent amount of dichloro-p-phenylenediamine copper (II) is used in a 10 layer between the paper support and the light-sensitive layer. Cyan dye images are produced similar to those obtained in Examples 1 and 2. The copper complex in this example is black and the layer containing it serves as an anti-halation coating as well as providing a source of color developing agent when activated with the sodium carbonate solution.

' EXAMPLE 10 Example 8 is repeated using in place of dichloro-pphenylenediamine cadmium (II), an equivalent amount of dichloro-p-phenylenediamine lead (II) in the layer between the paper support and the light-sensitive layer. Cyan dye images are obtained with substantially no difference between dye images in the incubated element and the control element.

EXAMPLE 11 Examples 1 and 2 are repeated using in place of dichloro-p-phenylenediamine cadmium (II), an equimolar amount of dichloro-l-(N,N-diethyl)-3-methyl4-phenylenediamine cadmium (II). Cyan dye images are obtained similar to those obtained in Examples 1 and 2.

EXAMPLE 12 Example 3 is repeated but using instead of the cadmium chloride complex of p-phenylenediamine dihydrogen chloride (i.e., p-chenylenediaminium tetrachlorocadmiumate II), an equivalent amount of 1-(N,N- diethyl) 3 methyl 4 phenylenediaminurn trichloroaquocadmiumate (II). A cyan dye image is found similar to that produced in Example 3. Similar results are obtained using equivalent amounts of l-(N-ethyl-N-phydroxyethyl) 3 methyl 4 phenylenediaminium dichlorosulfatocadmiumate II or an equivalent amount of 1 (N,N diethyl) 3 l3 methanesulfonamidoethyl- 4-phenylenediaminium tetrachlorocadmiumate (II) in place of p-phenylenediaminum tetrachlorocadmiumate (II) in Example 3.

EXAMPLE 13 A paper support is coated on one side in succession with (1) a gelatin layer containing a dispersion of dichloro-p-phenylenediamine cadmium (II) (prepared as described in Example 1), (2) a gelatin layer containing an ordinary gelatino-silver chlorobromide emulsion that is blue-sensitive and contains a nondiifusible yellow-dyeforming coupler of the type described in McCrossen et al. US. Pat. 2,875,057, (3) a gelatin layer containing an ordinary gelatino-silver chlorobromide emulsion that is green-sensitized and contains a nondiffusible 5-pyrazolone magenta-dye-forming coupler of the type described in Loria et al. US. Pat. 2,600,788 and (4) a gelatin layer .containing an ordinary gelatino-silver chlorobromide emulsion that is red-sensitized and contains a nondifusible cyan-dye-forming coupler of the type described in Fierke US. Pat. 2,801,171. The dichloro-p-phenylenediamine cadmium (II) is coated so that the mole ratio of this complex to the total silver halide is about 3:1. The element is exposed to an original color image, then contacted with a solution of 50 g. of sodium carbonate per liter of water until the color image comprising a yellow, magenta, cyan dye image along with a silver image is obtained. The developed photographic element is treated with a conventional acid stop bath, washed, treated with a conventional alkali metal ferricyanide bleach bath, followed by a conventional alkali methal thiosulfate fixing bath, washed and dried. A multicolor dye image reproduction of the original color image is obtained in the processed element.

Similar results are obtained when the light-sensitive layer in the photographic element of Example 13 are arranged in other orders over the gelatin layer containing one or more of our photographically compatible and inert color developing agent precursors 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 and 14.

EXAMPLE 14 Example 13 is repeated except that the dispersion of our color developing agent precursor dichloro-p-phenylenediamine cadmium (II) in gelatin is dispersed in the light-sensitive layers instead of being coated in a separate layer between the support and the blue-sensitive silver halide emulsion layer. The precursor is coated in each layer so that the mole ratio of precursor to silver in each layer is about 3:1. A multicolor image reproduction is produced when this element is exposed and processed as described in Example 13.

Similar results are obtained when Examples 13 and 14 are repeated using a conventional film support in place of a paper support.

The alkaline activator solution used for processing our photographic elements is advantageously made alkaline with any of the alkaline compounds conventionally used in photographic processing solutions, including the alkali metal hydroxides, alkali metal carbonates, borax, etc. Other addenda that are found in color developer solu tions, such as, silver halide solvents, antifoggants, development accelerators, stabilizers, chemical buifers, etc., are used to advantage in our activator solutions. Thickeners used in making viscous processing compositions are used to advantage in our activator solutions. Our photographic element is advantageously developed by contacting it with the activator solution until the active developing agent is released and the latent image in the silver halide is developed to silver and dye images. The activator solution is applied in viscous form or in liquid form by roller application, by brushing, by immersion, by transfer from a hydrophilic colloid web wet with imbibed solution, etc.

The preparation of color devolping agent precursor Nos. 1, 6 and is described in Chem. Abstracts, 52 page 4335, and the preparation of color developing agent precursor No. 9 is described in Chem. Abstracts, 55, page 2655. These references have no concept of photography or the use of the immediate compounds as inactive developing agent precursors. The Chem. Abstracts, 55, page 2655 reference states that the cadmium chloride complexes of diamines hydrolyzed very slowly (even with boiling dilute sodium hydroxide). It is unexpected from this reference that the immediate compounds would be activatable and release enough developing agent to develop a silver and dye image when treated at room temperature for only 2 or 3 minutes with our alkaline activator solutions.

Our light-sensitive silver halide elements containing our photographically inert complexes of polyvalent metal salts with p-phenylenediamine color developing agents as precursors for color developing agents have good stability upon storage; however, our precursors in the elements are easily and rapidly activated and silver and dye images developed by treating with alkaline solutions.

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

We claim: I

1. A photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondiffusible color-forming coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing a photographically compatible inactive color developing agent precursor that is the water insoluble, precipitated reaction product of (1) a water-soluble salt of a polyvalent metal and (2) a water-soluble and dilfusible p-phenylene-diamine color developing agent.

2. A photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondiffusible color-forming coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing a photographically compatible inactive color developing agent precursor that is the water insoluble, precipitated reaction product of (1) a water-soluble salt of a polyvalent metal and (2) a water-soluble and diffusible p-phenylenediamine color developing agent having the formula:

IIIH:

ll Rr R wherein R, R R and R each represent a member selected from the class consisting of hydrogen, an alkyl group having from 1 to 5 carbon atoms, an alkoxy group having from 1 to 5 carbon atoms and an acetamido group.

3. A photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondiifusible color-forming coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing a photographically compatible inactive color developing agent precursor that is the water insoluble, precipitated reaction product of (1) a water-soluble polyvalent metal salt and (2) a water soluble and diifusible pphenylenediarnine color developing agent having the formula:

N R2 R1 wherein R, R R and R each represent a member selected from the class consisting of hydrogen, an alkyl group having from 1 to 5 carbon atoms, an alkoxy group having from 1 to 5 carbon atoms and an acetamido group; X represents an anion; m represents the valence of said anion, an integer of 1 or 2; and n represents an integer of from 1 to 3.

4. A photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondirlusible color-forming coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing a water insoluble, precipitated photographically compatible inactive color developing agent precursor selected from those having the formula:

NHz +014) l wherein M represents a polyvalent metal; q represents an integer of 2 or 3 that is equal to the valence of M; r

represents an integer of 1 or 2; R, R R and R each represent a member selected from the class consisting of hydrogen, an alkyl group having from 1 to carbon atoms, an alkoxy group having from 1 to 5 carbon atoms and an acetamido group; X represents an anion; m represents an integer of l or 2 that is the valence of X; n is an integer of from 1 to 3; X; represents an anion; p represents an integer of 1 or 2 that is the valence of X and z represents an integer of from 1 to 5.

5. A photographic element of claim 2 in which said color developing agent precursor is in a hydrophilic colloid layer that is contiguous to and between said hydrophilic colloid layer containing said silver halide and said support.

6. A photographic element of claim 2 in which said color developing agent precursor is in said hydrophilic colloid layer containing said silver halide and said colorforming coupler.

7. A photographic element of claim 4 in which q is 2 and r is 1.

8. A photographic element of claim 4 in which q is 2 and r is 2.

9. A photographic element of claim 4 in which in is 1; nis 1 and qis2.

10. A photographic element of claim 4 in which m is l;nis2andqis2.

11. A photographic element of claim 4 in which m is l' nis3andqis2.

12. In a multilayer, multicolor photographic element comprising a support having thereon a red-sensitive silver halide hydrophilic colloid layer containing a non-diffusible cyan-dye-forming coupler that reacts with an oxidized aromatic primary amine color developing agent to form a cyan dye, a green-sensitive silver halide hydrophilic colloid layer containing a nondifl usible magenta-dye-forming coupler tha reacts with an oxidized aromatic primary amine color developing agent to form a magenta dye, and a blue-sensitive silver halide hydrophilic colloid layer containing a nondilfusible yellow-dye-forming coupler that reacts with an oxidized aromatic primary amine color developing agent to form a yellow dye, the improvement comprising the incorporation in at least one hydrophilic colloid layer contiguous to at least one of said silver halide hydrophilic colloid layers of a water insolube, precipitated photographicaly compatible inactive color developing agent precursor having the formula:

R3 R (Has) (X- wherein M represents a polyvalent metal; q represents an integer of 2 or 3 that is equal to the valence of M; r represents an integer of 1 or 2; R, R R and R each represent a member selected from the class consisting of hydrogen, an alkyl group having from 1 to 5 carbon atoms, an alkoxy group having from 1 to 5 carbon atoms and an acetamido group; X represents an anion; m represents an integer of 1 or 2 that is the valence of X; n is an integer of from 1 to 3; X; represents an anion; p represents an integer of l or 2 that is the valence of X and z represents an integer of from 1 to 5.

13. A photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondiffusible coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing a cadmium chloride complex of a p-phenylenediamine as a color developing agent precursor.

14. A photographic element comprising a support coated with at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nonditfusible coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing N Hz CdClz 15. A photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondiffusible coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing NHz CdClz ZHCl 16. A photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondiflFusible coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing ZnClz 17. A photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondifiusible coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and one the same side of said support at least one hydrophilic colloid layer containing 18. A photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondiffusible coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing CuClz 19. A process for producing a photographic dye image in an imagewise exposed photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nonditfusible color-forming coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing a photographically compatible inactive color developing agent precursor that is the water insoluble, precipitated reaction product of 1) a water-soluble salt of a polyvalent metal and (2) a water-soluble and diffusible p-phenylenediamine color developing agent, said process comprising contacting said element with an aqueous alkaline activator solution which causes said inactive color developing agent precursor to release said water-soluble and diifusible p-phenylenediamine color developing agent from said precursor, imagewise developing silver halide with the said released color developing agent to silver, and imagewise reacting resulting oxidized color developing agent with said color-forming coupler to produce a photographic dye image.

20. A process for producing a photographic dye image in an imagewise exposed photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondiffusible color-forming coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least on hydrophilic colloid layer containing a water insoluble, precipitated photographically compatible inactive color developing agent precursor having the formula:

NHz

wherein M represents a polyvalent metal; q represents an integer of 2 or 3 that is equal to the valence of M; r represents an integer of 1 or 2; R, R R and R each represent a member selected from the class consisting of hydrogen, an alkyl group having from 1 to 5 carbon atoms, an alkoxy group having from 1 to 5 carbon atoms and an acetamido group; X represents an anion; m represents an integer of l or 2 that is the valence of X; n is an integer of from 1 to 3; X represents an anion; p represents an integer of 1 or 2 that is the valence of X and z represents an integer of from 1 to 5, said process comprising contacting said element with an aqueous alkaline activator solution having a pH of at least about 10 which causes aid inactive color developing agent precursor to release said water soluble and diifusible p-phenylenediamine color developing agent, imagewise developing silver halide with the said color developing agent to silver, and imagewise reacting resulting oxidized color developing agent with said color-forming coupler to produce a photographic dye image.

21. A process for producing a photographic dye image corresponding to a latent image in a photographic element comprising a support having thereon at least one hydrophilic colloid light-sensitive silver halide layer containing contiguous to said silver halide a nondifrusible color-forming coupler that is capable of coupling with oxidized aromatic primary amine color developing agent to form a dye, and on the same side of said support at least one hydrophilic colloid layer containing lTIHz 22. A light-sensitive photographic element according to claim 1 in which said one hydrophilic colloid layer containing said photographically compatible inactive color developing agent precursor lies adjacent said one hydrophilic colloid silver halide nondiffusible layer containing said nondiifusible color-forming coupler.

23. A photographic element of claim 2 in which said color developing agent precursor is in a hydrophilic colloid layer contiguous to said silver halide containing hydrophilic colloid layer.

24. A photographic element of claim 2 in Which said color developing agent precursor is precipitated entirely in a hydrophilic colloid layer contiguous to said silver halide containing hydrophilic colloid layer.

References Cited UNITED STATES PATENTS 2,695,234 11/1954 Jaeken et al. 96-66.4 3,295,978 1/1967 Barr 9695 3,342,597 9/1967 Harnish et al. 9655 13,342,599 9/ 1967 Reeves 9695 OTHER REFERENCES Prasad et al.: Chemical Abstracts, vol. 55, pages 2654- J. TRAVIS, BROWN, Primary Examiner US. Cl. X.R.