US3607278A - Photographic elements containing fogged and unfogged silver halide grains and a slow silver halide emulsion layer - Google Patents

Photographic elements containing fogged and unfogged silver halide grains and a slow silver halide emulsion layer Download PDF

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Publication number
US3607278A
US3607278A US722223A US3607278DA US3607278A US 3607278 A US3607278 A US 3607278A US 722223 A US722223 A US 722223A US 3607278D A US3607278D A US 3607278DA US 3607278 A US3607278 A US 3607278A
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Prior art keywords
silver halide
grains
latent image
halide grains
layer
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US722223A
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Joseph R Ditzer Jr
Fred W Spangler
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Eastman Kodak Co
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Eastman Kodak 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
    • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer

Definitions

  • This invention relates to photographic materials, their preparation, and use.
  • this invention relates to a photographic element comprising fogged internal image silver halide grains, unfogged surface latent image grains and an unfogged fog-inhibiting layer, which element exhibits good fogresistance on development.
  • this invention relates to a photographic element imparting fog reduction in developer solutions and comprising layers having fogged internal latent image grains, unfogged surface latent image grains and a silver halide emulsion layer comprising silver halide grains exhibiting photographic sensitivity which is substantially lower than the sensitivity of the unfogged surface latent image grains.
  • antifoggants used to reduce fog to tolerable limits are soluble bromides, iodide ions and chloride ions, the latter used on silver chloride emulsions (Mees, The Theory of the Photographic Process, page 344).
  • iodide ions in the developer do not act as an antifoggant but cause an increase in fog.
  • silver halide crystals of the type employed in photographic emulsions have both surface and internal light sensitivity and that these types of sensitivity can vary considerably among different emulsions.
  • Silver halide grains having a high ratio of surface-to-internal sensitivity comprise the silver halide grains used in the majority of photographic emul SlOl'lS. V M
  • Another object of this invention is to provide photographic elements which exhibit high sensitivity and contrast and have improved fog resistance upon development in continuous developer systems.
  • Still another object of this invention is to provide improved photographic elements comprising surface latent image iodide-containing silver halide grains and fogged internal latent image silver halide grains.
  • This element comprises a support, unfogged surface latent image iodide-containing silver halide grains adjacent to fogged internal latent image silver halide grains and layer (1) comprising unfogged silver halide grains in which said halide comprises less than about 10 mole percent iodide and having photographic surface sensitivity which is less than about onetenth that of said surface image silver halide grains.
  • the substantially iodide-free layer (I) has a relatively slower speed or surface sensitivity than the surface image silver halide grains.
  • slower speed is meant that relatively no visible image is produced in said layer upon exposure and development of the unfogged surface latent image silver halide grains.
  • This layer (I) preferably comprises at least about 30 to about 65 mole percent chloride the remainder being bromide.
  • the silver halide grains used in this invention in other than layer (I) can thus comprise blends or mixtures of unfogged iodide containing surface image grains and fogged internal image grains, or these two types of grains can be coated in discrete layers which are in close proximity, i.e., in contiguous layers of the photographic element.
  • any one of the emulsion layers can be coated on top, since the fogged internal image grains in emulsion form or the slower speed layer have sufficient transparency to enable the surface image grains to be placed closest to the support and still receive sufficient transmitted radiation for exposure. Exposure of the unfogged surface image grains placed closest to the support can also be made through the support where this is transparent.
  • thesurface image grains are preferably coated over the fogged internal grains.
  • two types of the above grains i.e., surface image and internal image
  • the slow-speed layer having from less than about 10 mole percent iodide, e.g. 0 to about 10 mole percent iodide can thus be disposed in virtually any position on the element except between said other two types of grains.
  • said layer can be above the support and beneath said two types of grains in emulsion or layer form or the like or above said two grain types or blends thereof.
  • the slower speed layer is placed directly adjacent to and beneath said fogged internal image grains.
  • various other layers can be intermediate to these layers and grains. Said intermediate layers can comprise subbing layers, protective layers and the like.
  • the unfogged light-sensitive silver halide layer is substantially slower in speed, i.e. less sensitive, than the higher speed surface image silver halide grains.
  • substantially slower is meant at least about one-tenth and preferably about one-hundredth of said higher speeds.
  • it can be even less sensitive if desired.
  • the combination of grains in emulsion layers and blends thereof as described above provide speed increases when processed in developers being moderately high in silver halide solvent action as well as in developers having little or no silver halide solvent activity.
  • speed increases of the surface latent image grains can be effected by the use of various addenda as set forth hereinafter.
  • the surface latent image grains used in the practice of this invention have a relatively high degree of surface sensitivity and relatively low internal sensitivity and contain about 0.5 to about 99 mole percent iodide while the internal image grains used have a high degree of internal sensitivity but relatively low surface sensitivity.
  • the surface latent image grains contain silver halide grains that have substantial surface sensitivity and form latent images on the surface thereof when exposed to light. Unlike the fogged silver halide internal latent image grains described herein, the surface latent image silver halide grains are substantially unfogged.
  • the photographic silver halides which can be used in the preparation of the surface latent image grains include, for example, silver bromiodide, silver chloroiodide, silver chlorobromoiodide, and the like, the preferred halide being bromoiodide.
  • suitable grains and emulsions that form latent images on the surface of the silver halide grains reference is made to Trivelli and Smith in-The Photographic Journal, Volume LXXX, July 1940, (pages 285-288).
  • such grains and their emulsions are those which, when measured according to normal photographic testing techniques by coating a test portion of the emulsion on a transparent support, exposing the test portion to a light intensity scale for a fixed time between 0.01 and 1 second and development for 6 minutes at 68 F.
  • Developer A as hereinafter defined, have a sensitivity, measured at a density of 0.1 above fog, greater than the sensitivity of an identical test portion of the same emulsions which has been exposed in the same way, bleached minutes in aqueous 0.3 percent potassium ferricyanide solution at 65 F., and developed for 5 minutes at 65 F.
  • Developer A is the usual type of surface image developer and Developer B is an internal developer having high silver halide solvent activity.
  • the degree of internal sensitivity of the surface latent image grains is subject to wide variation.
  • the surface latent image grains and their emulsions can have relatively little internal sensitivity or they can have a fair amount of internal sensitivity, but preferably not greater than the surface activity.
  • the surface latent image grains can have high or low contrast since useful effects can be obtained with both types of emulsions.
  • the surface latent image grains can also be characterized as having a Dmax. greater than about 0.50 when coated at a coverage of about 540 mg. silver per square foot, exposed to a step wedge and processed for 12 minutes in Developer C as hereinafter define.
  • Particularly good results are obtained with surface image silver iodo-halide surface latent image grains such as silver bromoiodide emulsions.
  • Such emulsions can contain varying concentrations of iodide although especially useful results are obtained with such iodo-halide surface latent image grains containing from about 0.5 to about mole percent iodide.
  • the internal latent image photographic silver halide grains employed in the practice of this invention contain fogged internal latent image silver halide grains.
  • Any of the photographic silver halides can be used in the preparation of these internally fogged grains and include, for example, silver bromide, silver chlorobromoiodide, silver chlorobromide, silver chloride and the like.
  • suitable grains that form latent images internal to the silver halide grains reference is made to Davey and Knott US. Pat. No.
  • such grains and their emulsions are those which, when measured according to normal photographic techniques in their unfogged state by coating a test portion of the emulsion on a transparent support, exposing to a light intensity scale having a fixed time between 0.1 and 1 second, bleaching 5 minutes in 0.3 percent potassium ferricyanide solution at 65 F. and developing for about 5 minutes at 65 F.
  • the internal image grains employed in the practice of this invention are fogged partly or completely before use.
  • the fogging is generally sufficient to give a density of at least 0.50 when one mole (AgX) of the fogged emulsion is coated in a blend with 3 moles of surface image emulsion at a total coverage of about 540 mg. of silver per square foot and processed for 5 minutes in Developer B hereinafter described.
  • the surface Dmax. of the fogged internal image emulsions is generally less than about 0.30 when the emulsions are exposed to Dmax. and processed for 8 minutes in Developer C identified hereinafter.
  • the fogging of the internal image grains used in this invention can be effected using any method suitable for this purpose.
  • such fogging can be accomplished by exposing the grains to light.
  • Other methods such as chemical fogging methods can also be used.
  • the photographic silver halide grains having high internal fog but low surface sensitivity can also be prepared by fogging grains having both internal and surface sensitivity and then bleaching the surface image with a solution of potassium ferricyanide.
  • Another means of obtaining the fogged internal image grains is by exposure of nonfogged internal image grains to high energy radiation, such as X-rays.
  • the ratio between the surface latent image grains and the fogged internal image grains can be varied, depending upon the types of grains used, the contrast of the emulsions and other known variables. In general, quite useful results are obtained in those cases where the molar ratio of the surface image emulsion is at least equal to or greater than that of the fogged internal image grains. Useful results can be obtained even where the molar ratio, as explained above, is 42:1. Where the molar percent of the fogged internal image grains exceeds that of the surface image grains, such as 1:3 ratio,
  • the silver halide emulsions of a photographic element useful in this invention can contain conventional addenda such as gelatin plasticizers, coating aids, antifoggants such as the uzaindines and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis (sodium bisulfite), maleic dialdehyde, aziridines, dioxane derivatives, oxypolysaccharides and vinyl sulfonyl ethers.
  • Sensitizing dyes useful in sensitizing such emulsions are described, for example, in U.S. Pats. Nos.
  • Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.
  • Developing agents can also be incorporated into the silver halide emulsion if desired or can be contained in a separate underlayer.
  • the silver halide emulsion layers of a photographic element which are useful in the instant invention can contain any of the hydrophilic, water'permeable binding materials suitable for this purpose. Suitable materials include gelatin, colloidal albumin, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc. Mixtures of these binding agents can also be used.
  • the binding agents for the emulsion layer of the photographic element can also contain dispersed polymerized vinyl compounds. Such compounds are disclosed, for example, in US. Pats. Nos. 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of White issued July 6, 1965; 3,062,674 of I-louck, Smith and Yudelson issued Nov.
  • the silver halide emulsion layers of a photographic element which are useful in the instant invention can be coated on a wide variety of supports.
  • Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthalate) film and related films or resinous materials as well as glass, paper, metal and the like.
  • Supports such as paper which are coated with a-olefin polymers, particularly polymers of a-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylene-butene copolymers and the like can also be employed.
  • the speed of the photographic silver halide grains and their emulsions useful in the instant invention can be further increased by including in the emulsions a variety of hydrophilic colloids such as carboxymethyl protein of the type described in U.S. Pat. No. 3,011,890 of Gates, Jr., Miller and Koller issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Pat. No. 635,206 of Koller and Russell issued Jan. 23, 1962.
  • hydrophilic colloids such as carboxymethyl protein of the type described in U.S. Pat. No. 3,011,890 of Gates, Jr., Miller and Koller issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Pat. No. 635,206 of Koller and Russell issued Jan. 23, 1962.
  • Photographic silver halide grains and emulsions useful in the instant invention can also contain speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers. Frequently, useful effects can be obtained by adding the aforementioned speed-increasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emulsions.
  • speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers.
  • the photographic elements prepared according to the instant invention can be used in various kinds of photographic systems. In addition to being useful in X-ray and other nonoptically sensitized systems, they can also be used in orthochromatic, panchromatic and infrared sensitive systems.
  • the sensitizing addenda can be added to photographic systems before or after any sensitizing dyes which are used.
  • the invention can be used in emulsions intended for color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other colorgenerating materials, emulsions of the mixed-packet type such as described in U.S. Pat No. 2,698,794 of Godowsky issued Jan. 4, 1955; in silver dyebleach systems; and emulsions of the: mixed-grain type such as described in U.S. Pat. No. 2,592,243 ofCarroll and Hanson issued Apr. 8, 1952.
  • Silver halide emulsions useful in the instant invention can be chemically sensitized using any of the well-known techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium compounds and/or gold compounds.
  • the emulsions can also be chemically sensitized with salts of noble metals of group VIII of the periodic table which have an atomic weight greater than 100.
  • EXAMPLE 2 COATING A second coated sample is prepared as in example 1 except that a relatively light-insensitive silver chlorobromide gelatin emulsion having 40 mole percent chloride is coated in place of the gelatin underlayer at mg. Ag/ft".
  • EXAMPLE 3 COATING A third coating sample is prepared as in example 1 except that a chlorobromide emulsion having 40 mole percent chloride is coated in place of the gelatin underlayer at a coverage of 50 mg. Ag/ft In each of the above examples, the coatings are exposed on an Eastman 1B sensitometer and developed for 2 minutes at 98 F. in a series of surface image developers having the following formula and containing various concentrations of soluble iodide which approximate the iodide buildup in a partially exhausted developer solution.
  • a photographic element of claim 1 in which said unfogged surface latent image iodide-containing silver halide grains and said fogged internal latent image silver halide grains are each in discrete layers.
  • a photographic element of claim 1 in which said unfogged surface latent image iodide-containing silver halide grains and said fogged internal latent image silver halide grains are in one layer.
  • a photographic element of claim 1 in which said unfogged surface latent image iodide-containing silver halide grains and said fogged internal latent image silver halide grains are each in discrete layers farther from said support than said layer (1).
  • a photographic element of claim 1 in which said unfogged surface latent image iodide-containing silver halide grains and said fogged internal latent image silver halide grains are in one layer adjacent to said layer (I).
  • a photographic element of claim 1 in which said unfogged surface latent image iodide-containing grains and certain of said fogged internal latent image silver halide grains are in one layer and certain of said fogged internal latent image silver halide grains are in another layer other than layer (I).
  • layer (1) is disposed closer to said support than are said fogged grains.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US722223A 1968-04-18 1968-04-18 Photographic elements containing fogged and unfogged silver halide grains and a slow silver halide emulsion layer Expired - Lifetime US3607278A (en)

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BE (1) BE731674A (enrdf_load_stackoverflow)
DE (1) DE1912332A1 (enrdf_load_stackoverflow)
FR (1) FR2006427A1 (enrdf_load_stackoverflow)
GB (1) GB1257257A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941595A (en) * 1971-11-20 1976-03-02 Agfa-Gevaert, A.G. Photographic material containing fogged, direct positive silver halide emulsion and negative silver halide emulsion for the production of equidensities
US4082553A (en) * 1975-04-10 1978-04-04 Eastman Kodak Company Interimage effects with spontaneously developable silver halide
US4435500A (en) 1981-08-31 1984-03-06 Fuji Photo Film Co., Ltd. Method for developing silver halide photographic light-sensitive material
US4656120A (en) * 1982-12-27 1987-04-07 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US4818675A (en) * 1985-06-12 1989-04-04 Fuji Photo Film Co., Ltd. Silver halide photographic light sensitive material with improved silver blackness of picture image

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58215647A (ja) * 1982-06-09 1983-12-15 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2452765A (en) * 1942-09-02 1948-11-02 Eastman Kodak Co Multilayer photographic element having a mixed grain emulsion and process employing it
US2456956A (en) * 1942-02-09 1948-12-21 Eastman Kodak Co Photographic processes and lightsensitive elements therefor
US2996382A (en) * 1959-01-12 1961-08-15 Eastman Kodak Co Photographic elements having improved sensitivity
US3178282A (en) * 1959-01-12 1965-04-13 Eastman Kodak Co Photographic elements containing surface image and fogged internal image silver halide grains
US3206313A (en) * 1961-05-15 1965-09-14 Eastman Kodak Co Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity
US3490751A (en) * 1967-09-27 1970-01-20 Stoelling Brothers Co Stirring paddle assembly for process vat

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2456956A (en) * 1942-02-09 1948-12-21 Eastman Kodak Co Photographic processes and lightsensitive elements therefor
US2452765A (en) * 1942-09-02 1948-11-02 Eastman Kodak Co Multilayer photographic element having a mixed grain emulsion and process employing it
US2996382A (en) * 1959-01-12 1961-08-15 Eastman Kodak Co Photographic elements having improved sensitivity
US3178282A (en) * 1959-01-12 1965-04-13 Eastman Kodak Co Photographic elements containing surface image and fogged internal image silver halide grains
US3206313A (en) * 1961-05-15 1965-09-14 Eastman Kodak Co Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity
US3490751A (en) * 1967-09-27 1970-01-20 Stoelling Brothers Co Stirring paddle assembly for process vat

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941595A (en) * 1971-11-20 1976-03-02 Agfa-Gevaert, A.G. Photographic material containing fogged, direct positive silver halide emulsion and negative silver halide emulsion for the production of equidensities
US4082553A (en) * 1975-04-10 1978-04-04 Eastman Kodak Company Interimage effects with spontaneously developable silver halide
US4435500A (en) 1981-08-31 1984-03-06 Fuji Photo Film Co., Ltd. Method for developing silver halide photographic light-sensitive material
US4656120A (en) * 1982-12-27 1987-04-07 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US4818675A (en) * 1985-06-12 1989-04-04 Fuji Photo Film Co., Ltd. Silver halide photographic light sensitive material with improved silver blackness of picture image

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DE1912332A1 (de) 1969-10-23
FR2006427A1 (enrdf_load_stackoverflow) 1969-12-26
BE731674A (enrdf_load_stackoverflow) 1969-10-01
GB1257257A (enrdf_load_stackoverflow) 1971-12-15

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