Photographic recording material and process for development thereof

Abstract

 A photographic recording material for development in a rapid access developer is described which has improved raw stock keeping stability and improved latent image stability. A development process for the recording material is also described.

Description

[0001] The present invention relates to an improved photographic recording material for development in a rapid access process.

[0002] The formation of color photographic images by the image-wise coupling of oxidized primary aromatic amino color developing agents with color forming compounds to form indoaniline, indophenol, and azomethine dyes is well known. In such color image formation, the subtractive process of color formation is ordinarily used. The image dyes customarily formed are cyan, magenta, and yellow, which colors are, respectively, complementary to the primary colors, red, green and blue. Usually phenol or naphthol couplers are used to form cyan dye images; pyrazolone or cyanoacetyl derivative couplers are used to form magenta dye images; and acylacetamide couplers are used to form yellow dye images.

[0003] In these color photographic systems, the color-forming coupler may be either in the developer solution or incorporated in the photographic recording material. With the latter technique, the coupler is available in the emulsion layer during development to react with color developing agent that is oxidized by silver image development.

[0004] Color photographic recording materials often utilize silver halide emulsions of the high bromide type, including silver bromide, silver bromoiodide and silver chlorobromide emulsions. However, as explained in United States patent 4,269,927, high chloride silver halide photographic elements, that is, elements in which the silver halide grains are at least 90 mole percent silver chloride, possess a number of highly advantageous characteristics. For example, silver chloride possesses less native sensitivity in the visible region of the spectrum than silver bromide, thereby permitting yellow filter layers to be omitted from multicolor photographic elements. Furthermore, high chloride silver halides are more soluble than high bromide silver halides, thereby permitting development to be achieved in shorter times.

[0005] However, a problem with high chloride emulsions is their tendency toward reduced raw stock keeping stability and toward reduced latent image stability.

[0006] A further problem recognized with high chloride emulsions which contain sulfonated catechol compounds as sequestering agents concerns processing difficulties. These difficulties are related to reduced developability and speed losses with developer compositions that contain benzyl alcohol.

[0007] Accordingly, there is a need to provide a color photographic recording material which has improved raw stock and latent image keeping properties.

[0008] The present invention is based upon the provision of a photographic recording material which is characterized in that it comprises a support having thereon at least one high chloride silver halide emulsion layer and a reducing agent capable of enhancing raw stock and latent image stability, said recording material being intended for development in a rapid access developer composition which is substantially free of benzyl alcohol.

[0009] The compound capable of imparting raw stock and latent image stabilization to high chloride silver halide emulsions is a reducing agent which demonstrates a high level of compatibility with a high chloride silver halide emulsion and which causes no adverse affects on the emulsion layer or photographic recording material in which it is contained. Moreover, the reducing agent must be capable of being subjected to alkaline processing composition without causing adverse effects within either the photographic material in which it is contained or in the developer composition.

[0010] Typical reducing agents include reductone compounds, polyhydroxy aromatic compounds such as hydroquinone and catechol and aminophenols. A particularly preferred polyhydroxy aromatic compound is one having at least two hydroxy groups in ortho positions in relation to each other on an aromatic ring. Included within the class of polyhydroxy aromatic compounds which are useful in this invention are compounds of the benzene series and of the naphthalene series, which can be represented by the formula:

where X represents the carbon atoms necessary to complete a benzene or a naphthalene ring structure. In addition to the ortho hydroxyl substituents, the aromatic ring structure can be substituted with groups such as sulfo radicals, carboxy radicals, halogen atoms or additional hydroxy groups. Typical examples of polyhydroxy aromatic compounds useful in this invention include the following:
pyrocatechol,
4,5-dihydroxy-m-benzene disulfonic acid, disodium salt,
tetrabromopyrocatechol,
pyrogallol,
gallic acid,
methyl gallate,
propyl gallate,
2,3-dihydroxynaphthalene-6-sulfonic acid and 2,3,8-trihydroxynaphthalene-6-sulfonic acid.

[0011] In a preferred embodiment of this invention, the polyhydroxy aromatic compound is a dihydroxy­benzene disulfonate, such as for example 4,5-di­hydroxy-m-benzene disulfonic acid, dipotassium salt.

[0012] Polyhydroxy aromatic compounds have been used heretofore in photographic color developing compositions. For example, they are described in U. S. Patent 3,746,544 in combination with aminopolycarboxylic acid sequestering agents and in U. S. Patent 4,264,716 in combination with aminopolyphosphonic acid sequestering agents.

[0013] In U.S. Patent 4,269,927, noted above, these polyhydroxy aromatic compounds are described as sequestrants in silver halide emulsions to prevent fogging and desensitization caused by metal ion contamination. However, these compounds have not been used for that purpose because of loss of developability associated with use of developer compositions that contain benzyl alcohol. Moreover, their ability to overcome raw stock or latent image instability in high chloride emulsions has not been recognized in the art.

[0014] The term "reductone" refers to a class of unsaturated di-or-poly-enolic organic compounds which are strong reducing agents. They are generally Patents 2,423,730, 2,772,162, 2,895,826, 2,710,803, 2,407,207, 3,737,316 and 2,367,531. Loria et al U.S. Patents 2,722,161, 2,600,788, 3,006,759, 3,214,437 and 3,253,924, McCrossen et al U.S. patent 2,875,057, Bush et al U.S. Patent 2,908,573, Gledhill et al U. S. Patent 3,034,892, Weissberger et al U. S. Patents 2,474,293, 2,407,210, 3,062,653, 3,265,506 and 3,384,657, Porter et al U. S. Patent 2,343,703, Greenhalgh et al U. S. Patent 3,127,269, Feniak et al U.S. Patents 2,865,748, 2,933,391 and 2,865,751, Bailey et al U. S. Patent 3,725,067, Beavers et al U.S. Patent 3,758,308, Lau U. S. Patent 3,779,763, Fernandez U.S. Patent 3,785,829, U.K. Patent 969,921, U.K. Patent 1,241, 069, U. K. Patent 1,011,940, Vanden Eynde et al U. S. Patent 3,762,921, Beavers U.S. Patent 2,983,608, Loria U. S. Patents 3,311,476, 3,408,194, 3,458,315, 3,447,928, 3,476,563, Cressman et al U.S. Patent 3,419,390, Young U.S. Patent 3,419,391, Lestina U.S. Patent 3,519,429, U.K. Patent 975,928, U.K. Patent 1,111,554, Jaeken U.S. Patent 3,222,176 and Canadian Patent 26,251, Schulte et al U.K. Patent 1,248,924 and Whitmore et al U.S. Patent 3,227,550.

[0015] The photographic recording material can incorporate alkali-soluble ballasted couplers, as illustrated in U.S. Patents 3,716,368 and 2,722,163. The photographic elements can be adapted to form nondiffusible image dyes using dye-forming couplers in developers, as illustrated by U.K. Patent 478,984, Yager et al U.S. Patent 3,113,864, Vittum, et al U. S. Patents 3,002,836, 2,271,238 and 2,362,598, Schwan et al U.S. Patent 2,950,970, Carroll et al U.S. Patent 2,592,243, Porter et al U.S. Patents 2,343,703, 2,376,380 and 2,369,489, Spath U.K. Patent 886,723 and U.S. Patent 2,899,306, Tuite U.S. Patent 3,152,896 and Mannes et al U.S. Patents 2,115,394, 2,252,718 and 2,108,602, as described in Research Disclosure, December 1978, Item VII, the disclosure of which is hereby incorporated by reference.

[0016] Supports which can be used with the photographic recording materials of this invention include polymeric film, wood fiber - e.g. paper, metallic sheet and foil, glass and ceramic supporting elements provided with one or more subbing layers to enhance the adhesive, antistatic, dimensional, abrasive, hardness, frictional, antihalation and/or other properties of the support surface.

[0017] Typical of useful polymeric film supports are films of cellulose nitrate and cellulose esters such as cellulose triacetate and diacetate, polystyrene, polyamides, homo- and copolymers of vinyl chloride, poly(vinyl acetal), polycarbonate, homo- and copolymers of olefins, such as polyethylene and polypropylene, and polyesters of dibasic aromatic carboxylic acids with divalent alcohols, such as poly(ethylene terephthalate).

[0018] Typical of useful paper supports are those which are partially acetylated or coated with baryta and/or a polyolefin, particularly a polymer of an α-olefin containing 2 to 10 carbon atoms, such as polyethylene, polypropylene and copolymers of ethylene and propylene.

[0019] Polyolefins, such as polyethylene, polypropylene and polyallomers - e.g. copolymers of ethylene with propylene, as illustrated by Hagemeyer et al U.S. Patent 3,478,128 are preferably employed as resin coatings over paper, as illustrated by Crawford et al U.S. Patent 3,411,908 and Joseph et al U.S. Patent 3,630,740, over polystyrene and polyester film supports, as illustrated by Crawford et al U.S. Patent 3,630,742, or can be employed as unitary flexible reflection supports, as illustrated by Venor et al U.S. Patent 3,973,963.

[0020] Preferred cellulose ester supports are cellulose triacetate supports, as illustrated by Fordyce et al U.S. Patent 2,492,977, '978 and 2,739,069, as well as mixed cellulose ester supports, such as cellulose acetate propionate and cellulose acetate butyrate, as illustrated by Fordyce et al U.S. Patent 2,739,070.

[0021] Preferred polyester film supports are comprised of linear polyester, such as illustrated by Alles et al U.S. Patent 2,627,088, Wellman U.S. Patent 2,720,503, Alles U.S. Patent 2,779,684 and Kibler et al U.S. Patent 2,901,466. Polyester films can be formed by varied techniques, as illustrated by Alles, cited above, Czerkas et al U.S. Patent 3,663,683 and Williams et al U.S. Patent 3,504,075, and modified for use as photographic film supports, as illustrated by Van Stappen U.S. Patent 3,227,576, Nadeau et al U.S. Patent 3,501,301, Reedy et al U.S. Patent 3,589,905, Babbitt et al U.S. Patent 3,850,640, Bailey et al U. S. Patent 3,888,678, Hunter U. S. Patent 3,904,420 and Mallinson et al U.S. Patent 3,928,697.

[0022] The photographic elements can employ supports which are resistant to dimensional change at elevated temperatures. Such supports can be comprised of linear condensation polymers which have glass transition temperatures above about 190°C, preferably 220°, such as polycarbonates, polycarboxy­lic esters, polyamides, polysulfonamides, polyethers, polyimides, polysulfonates and copolymer variants, as illustrated by Hamb U.S. Patents 3,634,089 and 3,772,405, Hamb et al U. S. Patents 3,725,070 and 3,793,249, Wilson Research Disclosure, Vol. 118, February 1974, Item 11833 and Vol. 120, April 1974, Item 11833, and Vol. 120, April 1974, Item 12046, Conklin et al Research Disclosure, Vol. 120, April 1974, Item 12012, Product Licensing Index, Vol.92, December 1971, Items 9205 and 9207, Research Disclosure, Vol. 101, September 1972, Items 10119 and 10148, Research Disclosure, Vol. 106, February 1973, Item 10613, Research Disclosure, Vol. 117, January 1974, Item 11709 and Research Disclosure, Vol. 134, June 1975, Item 13455, and as described in Research Disclosure, December 1978, Item XVII, the disclosures of which are hereby incorporated by reference.

[0023] Other features including chemical or spectral sensitization, the use of addenda such as antifoggants and stabilizers, vehicles and vehicle extenders, coating aids, hardeners, antistatic layers and processing techniques can be found n Research Disclosure,December 1978, No. 17643, the disclosure of which is hereby incorporated by reference.

[0024] Processing of exposed photographic recording material is accomplished in a three-step operation, color development (45 sec, 35°C), bleach-fix (45 sec, 35°C) and stabilization or water wash (90 sec, 35°C) followed by drying (60 sec, 60°C).

[0025] The formulations for the above solutions are:

1) Color developer:
Lithium salt of sulfonated polystyrene	0.25 mL
Triethanolamine	11.0 mL
N,N-diethylhydroxylamine (85% by wt.)	6.0 mL
Potassium sulfite (45% by wt.)	0.5 mL
Color developing agent (4-(N-ethyl-N-2 methanesulfonylaminoethyl)-2-methylphenylenediaminesesquisulfate monohydrate)	5.0 g
Stilbene compound stain reducing agent	2.3 g
Lithium sulfate	2.7 g
Potassium chloride	2.3 g
Potassium bromide	0.025 g
Sequestering agent	0.8 mL
Potassium carbonate	25.0 g
Water to total of 1 liter, pH adjusted to 10.12

2) Bleach-fix:
Ammonium thiosulfate	58. g
Sodium sulfite	8.7 g
Ethylenediaminetetraacetic acid ferric ammonium salt	40. g
Acetic acid	9.0 mL
Water to total 1 liter, pH adjusted to 6.2

3) Stabilizer:
Sodium citrate	1 g
Water to total 1 liter, pH adjusted to 7.2

[0026] The developing composition exhibited excellent stability and the process provided excellent results, even though the total wet time was only three minutes, and thus achieved the objective of high quality rapid-access processing, which is especially useful in a "mini-lab" facility.

[0027] An important feature of this invention is that in processing the described photographic recording material there is minimal development restraint which permits rapid access processing. Moreover, the rapid access processing does not require high development temperatures.

Claims

1. A photographic recording material for development in a rapid access developer composition which is substantially free of benzyl alcohol, said material being characterized in that it comprises a support having thereon at least one layer comprising a high chloride silver halide emulsion and a raw stock, latent image stabilizing reducing agent compound.

2. The photographic recording material of claim 1 wherein the reducing agent is a polyhydroxy aromatic compound.

3. The photographic recording material of claim 2 wherein the reducing agent has the structural formula

where X represents the carbon atoms necessary to complete a benzene or a naphthalene ring.

4. The photographic recording material of claim 2 wherein the reducing agent is a sulfonic acid substituted o-dihydroxy benzene compound.

5. The photographic recording material of claim 1 wherein the reducing agent is present in an amount of from about 0.05 to about 50 g thereof per mole of silver.

6. The photographic recording material of claim 5 wherein the reducing agent is present in an amount of from about 0.25 to about 30 g thereof per mole of silver.

7. The recording material according to claim 1 which also comprises a color image-forming compound.