US3495983A - Photosolubilization process using phenols as dmax maintainers - Google Patents

Photosolubilization process using phenols as dmax maintainers Download PDF

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US3495983A
US3495983A US653590A US3495983DA US3495983A US 3495983 A US3495983 A US 3495983A US 653590 A US653590 A US 653590A US 3495983D A US3495983D A US 3495983DA US 3495983 A US3495983 A US 3495983A
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silver halide
silver
image
solution
maintainers
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Jack Freshwater Strange
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/492—Photosoluble emulsions
    • 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
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing

Definitions

  • the invention of this application is concerned with a process of forming a silver halide image by selectively exposing a photosoluble silver halide layer and dissolving the exposed photosoluble silver halide in a silver halide solvent, said process being characterized by having present, during treatment in the solvent, a D -maintaining amount of a phenolic compound devoid of ionizable iodine, or oxidizing or reducing groups which are active at the working pH, preferably a mononuclear phenol having a hydrocarbon substitutent in the o-position selected from the group consisting of o-phenylphenol and o-allylphenol.
  • This invention relates to a process for forming images from photosoluble (photosolubilizable) silver halide layers.
  • the present invention constitutes an improvement in a silver halide photosolubilization process by the use of a phenolic compound adjuvant which helps to prevent dissolution of silver halide in unexposed areas while allowing dissolution to proceed in the exposed areas. Because of this characteristic, the adjuvant can be characterized as a maximum density maintainer, or D maintainer.
  • This invention pertains to an improvement in a photosolubilization process of forming -a direct positive silver halide image which process comprises (a) exposing, imagewise, a photosoluble layer containing silver halide made relatively less soluble in a silver halide solvent by treatment with an organic compound containing sulfur and/ or nitrogen, and capable of form- 3,495,983 Patented Feb. 17, 1970 ing a silver salt of lower solubility in Water than silver chloride, and
  • the improvement being characterized by the presence while said layer is in the bath at pH 4-11, preferably 7-10, of D -maintaining amounts of an aromatic hydroxy compound having at least one benzene ring containing a phenolic hydroxyl group, including unsubstituted phenol and naphthols and said compounds substituted with alkyl, e.g., methyl, ethyl, and isopropyl; vinyl, allyl; alkoxy, e.g., methoxy; carboxy; benzoyl, or aryl, e.g., phenyl, or a hydrolyzable precursor of the compound,
  • a photosoluble silver halide layer as defined in Blake US. 3,155,- 519, preferably a layer of silver chloride emulsion insolubilized with 2-mercapto-4-phenylthiazole or a related mercaptan as disclosed in said patent is prepared.
  • the element may advantageously have a photographic optical sensitizing dye associated with its silver halide crystals as disclosed in assignees copending application of Blake, U.S. Ser. No. 390,460, filed Aug. 18, 1964 (US.
  • the photosoluble layer is exposed, imagewise, to actinic radiation and then treated in an aqueous bath comprising from 0.1 to 2 moles per liter of a thiosulfate, e.g., sodium thiosulfate, silver halide solvent and a phenolic D maintainer as defined above.
  • a particularly preferred D maintainer is o-phenylphenol in a concentration of 0.1 to 1.0 g./liter, preferably from .4 to .6 g./liter.
  • the time and temperature of treatment in the aqueous bath are obviously dependent variables but at a temperature of 70 F. the time should be about 1 to 5 minutes.
  • This treatment removes silver halide from the exposed areas at a much faster rate than from the unexposed areas, leaving a positive silver halide image.
  • the presence of an organic compound such as o-phenylphenol further lowers the rate of dissolution of the unexposed silver halide, relative to that of the exposed silver halide, contributing to better image formation, especially to higher densities in unexposed areas.
  • a useful positive image can be produced, particularly for viewing by projection, by this single treatment, although a washing step is generally used.
  • it is desirable to intensify the silver halide image usually by treating with a photographic silver halide developer solution to reduce the image to one of black metallic silver.
  • the silver halide image may be fogged prior to reduction by flashing to white light or, more conveniently, by use of a prefogged element such as described in assignees copending applications, Blake U.S. Ser. No. 629,426 filed Apr. 10, 1967 and Haugh U.S. Ser. No. 478,421 filed Aug. 9, 1965.
  • Other methods of intensifying the silver halide image e.g., by toning, color developing, etc., are disclosed in US. 3,155,507.
  • any of the various photosoluble silver halide elements described in the U.S. Patents and Blake and Haugh applications listed above can be used in the process of this invention. These, of course, may be modified as described in the patents and applications by variations in the silver halide, the binder (if present), the organic compounds for insolubilization of silver halide (whose utility can be established by the simple tests defined therein for determination of other useful compounds), the adjuvants generally employed in silver halide systems, the supports, and in the relative concentrations of the various components.
  • Various auxiliary layers may be present, such as abrasion over-coatings, subbing layers, and antihalation undercoats or backing layers.
  • the elements may include multilayer as well as monolayer structures.
  • the various layers, including the support may include inert ingredients, e.g., pigments, organic polymer latices, and matting agents.
  • inert ingredients e.g., pigments, organic polymer latices, and matting agents.
  • the silver halide may be insolubilized by treatment with an appropriate organic compound either during emulsion manufacture or by treatment of the coated element with a solution of the organic compound.
  • the phenolic compound should be devoid of ionizable iodine because the iodide ion readily replaces the organic compound of step (a) to form silver iodide; it should be devoid of oxidizing groups because these tend to oxidize the silver salts of organic compound of step (a) so that exposed and unexposed areas cannot be easily distinguished in terms of their rates of solution in a silver halide solvent.
  • the dissolution developer i.e., the solution of silver halide solvent
  • the essential components for this invention are water, silver. halide solvent and a D maintainer. Numerous useful silver halide solvents are given in US. Patent 3,155,507 but in this application the use of preferred silver halide solvents containing the thiosulfate anion will be described.
  • EXAMPLE I A light-sensitive gelatino-silver chloride coagulum, made by precipitation and coagulation washing in the manner taught in Moede, U .8. Patent 2,772,165, was redispersed in an aqueous gelatin solution so as to achieve a gelatin to silver chloride weight ratio of 0.79. The resulting emulsion was digested at 170 F. for 20 minutes in the presence of 0.80 g. of Z-mercapto-4-phenylthiazole and 0.025 g. of the dye of Example I of Kendall 2,342,- 546 per mole of silver chloride.
  • emulsion adjuvants were added, including gelatin hardening agents and coating aids, and the emulsion was coated on a vinylidene chloride copolymer subbed polyester base prepared as described in Example IV of Alles, US. Patent 2,779,- 684 (and to which a gelatin sub-layer had been subsequently applied).
  • the coating weight was 46 mg./dn'1. calculated as metallic silver.
  • a sample of the dried photosoluble film was exposed through a /2 stepwedge for 15 seconds a 24 inches distance from a high intensity, tungsten filament, incandescent lamp (General Electric Reflector Photoflood lamp, N0. PH/RFL 2).
  • the exposed film serving as a control, was then processed for 3 minutes at 68 F. in a dissolution developer consisting of an aqueous solution containing 57.5 g./liter of sodium thiosulfate adjusted to a pH of 9.0 with 3 N H 80
  • a second sample of the identically exposed film was treated similarly except that, per liter of dissolution developer, there was added 10 ml.
  • the films were then washed in water for 3 minutes and dried in air.
  • the intensified metallic silver image of the control film had a maximum transmission optical density of 2.94 while the film treated with D maintainer had a densty of over 4.0, i.e., a density greater than could be detected by the densitometer.
  • the minimum densities were approximately the same (about 0.04) in both films. Also the contrasts were essentially identical in the two films.
  • Example II Example I was repeated except that both the control and the experimental dissolution developers (i.e., the aqueous solutions of silver halide solvent) contained additionally 4.5 g./liter of anhydrous Na SO Both solutions were adjusted to pH 9.0 with 3 N H SO
  • the film processed in the solution containing o-phenylphenol again had a D above but increased in apparent positive speed, i.e., optical densities began decreasing at steps corresponding to lower exposure, than the films in Example I.
  • the D was only 0.2 but an image was visible.
  • EXAMPLE III The following silver halide solvent solution was prepared for use as a dissolution developer.
  • the above solution was diluted with an equal volume of water (as a control) or with an equal volume of aqueous solution containing an organic compound as a D maintainer as noted in the table above.
  • a number of D maintainers were tested by using such solutions in processing exposed film samples as described in Example I.
  • the samples were processed in solutions containing the Dmg,x maintainers at pH of 6.0, some at a concentration of 0.05 and others at a concentration of 0.1% by weight, processing for 2 minutes at 68 F.
  • the films were then washed, intensified, washed again and dried as in Example I.
  • the eifectiveness of the D maintainer is indicated by the increase in D (optical transmission density) over the control (D 1.36).
  • a photosoluble element was prepared by coating an aqueous gelatin dispersion of a spectrally sensitized silver chlorobromide (70 mole percent silver chloride and 30 mole percent silver bromide) which contained 0.67 gram of the insolubilizer, 2-mercapto-4-cyclohexylthiazole, per mole of silver halide, and the merocyanine dye of Example I of Kendall U.S.P. 2,342,546 on the film base described in Example I. The dried element was then exposed behind a V2 stepwedge for 5 seconds to the light source of Example I at a distance of about 20 inches.
  • a spectrally sensitized silver chlorobromide 70 mole percent silver chloride and 30 mole percent silver bromide
  • the dried element was then exposed behind a V2 stepwedge for 5 seconds to the light source of Example I at a distance of about 20 inches.
  • Exposed elements were immersed in a dissolution developer (compositions shown in Table II) for 30 seconds and 3 minutes, rinsed in water, reexposed, and bathed in a metol-hydroquinone intensifier (conventional photographic developer).
  • a dissolution developer compositions shown in Table II
  • the dissolution developers A and D serve as controls at pH l-(l-napthyl)-2-thiourea per mole of silver chloride was substituted for the benzoxazolethiol.
  • EXAMPLE VII A photosoluble element, with S-nitrobenzimidazole as insolubilizer, was prepared as described in Example VI of US. Patent 3,155,507. Film samples of the element were exposed and processed as in Example IV.
  • EXAMPLE VIII A photographic element was prepared by coating an aqueous gelatin dispersion of silver bromochloride (30 mole percent silver bromide and 70 mole percent silver chloride) on a film base prepared as in Example IV of Alles U.S.P. 2,779,684. After drying, the film was soaked for 30 seconds in a solution of 0.15 g. of 2,5- dimercapto-l,3,4-thiadiazole in 500 ml. ethanol-water solution (17 parts ethanol-3 parts water) to produce a photosoluble element. Exposure and processing were as The maximum transmission optical densities were then determined and are listed below.
  • EXAMPLE V A photosoluble element was prepared by coating an aqueous gelatin dispersion of a spectrally sensitized silver chloride which contained 1.18 grams of benzoxazolethiol per mole of silver chloride as insolubilizer and the merocyanine dye of Example I of Kendall U.S.P. 2,342,546 on the film base of Example I. The drided element was then exposed and processed as in Example IV.
  • Example V was repeated except that 2.4 grams of Dmax after described in Example IV with exposure times as indicated.
  • the color coupling developer solutions contained paminodiethylaniline hydrochloride as the silver halide developing agent.
  • the color coupler for the cyan developer solution was 2,4-dichloro-l-naphthol; for the yellow developer solution the color coupler was 2-methoxy-5- methacrylamido-Z-benzoylacetanilide.
  • the active agents were, respectively, K Fe(CN) and Na S O In both samples a multicolor image resulted from the superimposing of a negative-positive cyan image and a positive yellow image. At the low exposure steps, the image was yellow.
  • the sample processed with the D maintainer (ophenylphenol) exhibited an effective speed increase of three steps in the positive, high exposure (pure cyan) region of the image. This sample also showed better color difierentiation from step to step which is equivalent to more effective conveyance of information.
  • the increased positive speed is probably attributable to the high pH of the silver halide solvent solution (the first processing solution). Processing at such a high pH (9.0) in the abesnce of the D maintainer would have resulted in very severe loss of image density.
  • EXAMPLE X A silver chloride emulsion was prepared as described in Example I. Before coating, the emulsion was divided into a number of separate portions and various D maintainers were added, from siutable solvents, in the concentrations (expressed as grams of D maintainer per mole of AgCl) indicated in the table below. The portions were then coated as in Example I to give coating weights of 37 mg./dm. calculated as metallic silver. Samples of the coated films were exposed and treated for 2 minutes in the silver halide solvent solution used for the control film sample of Example IX to form positive silver chloride images.
  • the present invention has the advantages of the basic process of photosolubilization, especially that of a very simple, single step process of obtaining a positive image.
  • Advantages over the basic process include increased optical densities in unexposed or lightly exposed areas, both for silver halide images and for intensified images.
  • processing is simpler because the D maintainers make the effects of such variables as concentration of silver halide solvent, solution pH, processing times and temperatures less critical.
  • the D maintainers often increase contrast and apparent speed although decreases iri one or both of these variables sometimes occur.
  • Another method is available for controlling speed and contrast. Still other advantages will be apparent from the above description of the invention.
  • a photosolubilization process for forming a directpositive silver halide image which comprises:
  • said process being characterized by the presence while said layer is in said bath, at a predetermined pH, of D -maintaining amounts of an aromatic hydroxy compound containing at least one phenolic hydroxy group selected from the class consisting of unsubstituted phenol and naphthols and their alkyl; vinyl; allyl; alkoxy, carboxy, benzoyl, and aryl substituted derivatives, and their hydrolyzable precursors,
  • said aromatic hydroxyl compound being present in the range of 0.1 to 20 g./liter of the aqueous bath, to retard solution of the unexposed silver halide.
  • a process according to claim 2 wherein said aromatic hydroxyl compound is o-phenylphenol.
  • step (a) is present in such an amount, in terms of the ratio of its weight to the surface area of the silver halide crystals, that when admixed in such ratio with an aqueous silver bromochloride, 30/70 mole percent, gelatin dispersion containing 0.29 mg. of Ag in one-half ml., and said silver bromochloride dispersion is treated with 10% by weight aqueous sodium thiosulfate, so that the resulting mixture contains 0.29 mg. of Ag and 100 mg.
  • a photosoluble layer containing light-sensitive silver halide made less soluble in a silver halide solvent by treatment with an organic compound containing sulfur and/or nitrogen and capable of forming a silver salt of lower solubility in water than silver chloride, said layer containing in addition a different auxiliary organic compound and which is a phenolic compound devoid of ionizable iodine, or oxidizing or reducing gI'Oups which are active at the working pH, in sufiicient quantity to further retard solution of unexposed silver halide in said layer.
  • auxiliary compound is an aromatic hydroxyl compound containing at least one phenolic hydroxyl group, said compound being selected from the class consisting of unsubstituted phenol and naphthols and their alkyl, vinyl, allyl, alkoxy, carboxy, benzoyl and aryl-substituted derivatives and their hydrolyzable precursors.
  • a layer according to claim 7 wherein said auxiliary compound is o-phenylphenol.
  • a layer according to claim 7 wherein said auxiliary compound is o-allylphenol.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US653590A 1967-06-23 1967-06-23 Photosolubilization process using phenols as dmax maintainers Expired - Lifetime US3495983A (en)

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US64825067A 1967-06-23 1967-06-23
US65359067A 1967-06-23 1967-06-23
US64822967A 1967-06-23 1967-06-23

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US648229A Expired - Lifetime US3493373A (en) 1967-06-23 1967-06-23 Photosolubilization image formation process with organic dmax. maintainers
US648250A Expired - Lifetime US3495982A (en) 1967-06-23 1967-06-23 Process for dissolution development using thiourea compounds as dmax maintainers

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3849133A (en) * 1970-04-20 1974-11-19 Fuji Photo Film Co Ltd Process for forming photographic images by high speed diffusion transfer process

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3628956A (en) * 1967-12-08 1971-12-21 Du Pont Process for preparing direct positive images by photosolubilization
US3652279A (en) * 1969-07-18 1972-03-28 Du Pont Nitrogen-containing dmax maintainers for use in photosoluble emulsions
US4031127A (en) * 1975-08-06 1977-06-21 Eastman Kodak Company Acyl hydrazino thiourea derivatives as photographic nucleating agents

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2230977A (en) * 1940-04-04 1941-02-04 American Cyanamid Co Single solution photographic developing and fixing bath
US3155507A (en) * 1961-12-08 1964-11-03 Du Pont Photographic processes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2230977A (en) * 1940-04-04 1941-02-04 American Cyanamid Co Single solution photographic developing and fixing bath
US3155507A (en) * 1961-12-08 1964-11-03 Du Pont Photographic processes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3849133A (en) * 1970-04-20 1974-11-19 Fuji Photo Film Co Ltd Process for forming photographic images by high speed diffusion transfer process

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US3493373A (en) 1970-02-03
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BE716966A (en:Method) 1968-12-23
GB1234993A (en) 1971-06-09

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