EP0226184A2 - Agent de contrôle pour le développement de germes dans des matériaux et procédés photographiques - Google Patents

Agent de contrôle pour le développement de germes dans des matériaux et procédés photographiques Download PDF

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Publication number
EP0226184A2
EP0226184A2 EP86117268A EP86117268A EP0226184A2 EP 0226184 A2 EP0226184 A2 EP 0226184A2 EP 86117268 A EP86117268 A EP 86117268A EP 86117268 A EP86117268 A EP 86117268A EP 0226184 A2 EP0226184 A2 EP 0226184A2
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EP
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Prior art keywords
silver halide
photographic
development
control agent
nucleation
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP86117268A
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German (de)
English (en)
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EP0226184A3 (fr
Inventor
Ismael Aldolfo§c/o EASTMAN KODAK COMPANY Olivares
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Eastman Kodak Co
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Eastman Kodak Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/09Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/061Hydrazine compounds

Definitions

  • This invention relates to a negative-working photographic silver halide element, process and developer composition comprising a nucleation development control agent which enables increased image discrimination and enables reduced image development spread beyond unexposed silver halide grains in close proximity to exposed silver halide grains in the photographic element.
  • High-contrast negative-working photographic silver halide photographic elements that is such elements which are capable of providing a developed image having a gamma higher than 10, are generally known as "lith" photographic elements.
  • Conventional lith photographic elements contain high chloride photographic silver halide emulsions, that is photographic silver halide emulsions containing at least 50 percent by weight silver chloride based on total silver halide in the photographic element, typically in the form of silver chlorobromides and silver chlorobromoiodides.
  • High contrast development of such exposed photographic elements is achieved by means of a phenolic developing agent, such as described by J.A.C. Yule in the Journal of the Franklin Institute, Vol. 239, pages 221-230 (1945).
  • High contrast negative-working photographic silver halide elements comprising nucleating agents are also known. Such elements are described in, for example, Canadian Patent 1,146,001 and U.S. 4,269,929. Such photographic silver halide elements are useful in the graphic arts, including photolithography. These elements upon exposure and processing involve nucleation development of an image.
  • high contrast negative-working photographic silver halide elements can comprise a nucleating agent in a concentration sufficient to increase contrast and sufficient to promote infectious, imagewise development of unexposed photographic silver halide grains in close proximity to exposed photographic silver halide grains. Nucleation development occurs in forming an image in such photographic silver halide elements.
  • Nucleation development in a negative-working photographic silver halide element comprising a nucleating agent herein means rendering unexposed photographic silver halide grains developable by means of forming developable sites on the surface of the unexposed silver halide grains by a reductive process.
  • a problem has been encountered in negative-working photographic silver halide elements comprising photosensitive silver halide grains capable of forming a surface latent image, and a nucleating agent, such as a hydrazide nucleating agent, in a concentration sufficient to increase contrast and sufficient to promote infectious, imagewise development of unexposed silver halide grains in close proximity to exposed silver halide grains.
  • the problem is that insufficient control of development during nucleation has been observed. As a result of insufficient control, development during nucleation spreads to an undesired extent to unexposed silver halide grains in close proximity to exposed silver halide grains in the photographic element. Insufficient control of nucleation development also results in less than desired image discrimination in the developed photographic element.
  • the need for nucleation development control is particularly important in negetive-working photographic silver halide elements comprising nucleating agents and chemically sensitized photographic silver halide.
  • nucleation development control agent that is an isothiuronium compound or a free mercaptan, in a concentration sufficient to (1) increase image discrimination and (2) reduce image development spread beyond unexposed silver halide grains in close proximity to exposed silver halide grains in a negative-working photographic silver halide element.
  • the present invention provides a negative working photographic element comprising a support bearing a photographic silver halide emulsion layer comprising photosensitive silver halide grains capable of forming a surface latent image, and a nucleating agent in a concentration sufficient to increase contrast and sufficient to promote infectious, imagewise development of unexposed silver halide grains in close proximity to exposed silver halide grains.
  • This photographic element comprises a nucleation development control agent as described.
  • a process according to the invention comprises development of an exposed negative-working photographic silver halide element comprising a support bearing a photographic silver halide emulsion layer comprising photosensitive silver halide grains capable of forming a surface latent image, and a nucleating agent in a concentration sufficient to increase contrast and sufficient to promote infectious, imagewise development of unexposed silver halide grains in close proximity to exposed silver halide grains.
  • This process is carried out in the presence of the nucleation development control agent which is an isothiuronium compound or a free mercaptan, which is in the developer solution and/or the photographic silver halide element, but preferably in the developer solution.
  • the process for example, comprises the step of: developing the photographic element in a silver halide aqueous alkaline developer solution at a pH of at least 10 comprising
  • a preferred nucleation development control agent is an isothiuronium compound represented by the formula: wherein
  • the nucleation development control agent enables increased image discrimination and reduced image development spread beyond the unexposed silver halide grains in close proximity to exposed silver halide grains. This is particularly advantageous in the graphic arts because the nucleation development control agents reduce image spread during processing thereby preserving the fine lines and sharp dots required in the graphic arts.
  • the nucleation development control agent also can reduce the occurence of spurious black spot fog, also designated as "pepper fog", in the photographic element.
  • R alkylene herein can be unsubstituted or substituted with groups that do not adversely affect the nucleation development control properties of the nucleation development control agent, including such groups as alkyl, aryl or oxygen or nitrogen containing groups, such as carboxyl, carbonyl, carbamyl, hydroxyl, ether and ester groups.
  • nucleation development control agents are isothiuronium sulfonate compounds which are represented by the formula: wherein
  • alkylene groups are methylene, ethylene, propylene, butylene and pentylene.
  • nucleation development control agents examples include:
  • the isothiuronium compounds are prepared by methods of synthesis known in the organic compounds synthesis art. Useful methods for preparing such compounds are described in, for example German Patent 1,031,303 and U.S. 2,833,781.
  • free mercaptan herein means a mercaptan nucleation development control agent in the free mercaptan form or in its mercaptan salt form which does not adversely affect the desired nucleation development control properties.
  • Preferred free mercaptan nucleation development control agents are represented by the formula: wherein
  • nucleation development control agents which are free mercaptan and/or mercaptan salt compounds are as follows:
  • the photographic silver halide grains in the photographic element are capable of forming a surface latent image, as opposed to being of the internal latent image-forming type photographic silver halide.
  • the photographic silver halide grains are preferably in the form of a photographic silver halide emulsion, particularly a gelatino emulsion.
  • Photographic silver bromide, silver bromoiodide, silver chlorobromide, silver chlorobromoiodide, silver chloride and other photographic silver halides capable of forming a surface latent image are examples of useful photographic silver halides.
  • the iodide content of the photographic silver halide is less than 10 mole percent silver iodide based on total silver halide.
  • the silver halide grains when the silver halide emulsions are to be used for lith applications, preferably have a mean grain size of not larger than 0.7 micron, particularly less than about 0.7 micron.
  • Silver coating coverages for photographic elements according to the invention generally are within the range of about 0.5 to about 10 grams per square meter of support.
  • Monodispersed silver halide emulsions have a large proportion of the silver halide grains falling within a narrow size-frequency distribution.
  • Monodispersed silver halide emulsions herein mean those silver halide emulsions in which at least 90 percent (by weight or by number) of silver halide grains are within plus or minus 40 percent of the mean grain size.
  • Emulsion layers are useful having silver halide grains of any conventional geometric form, such as regular cubic or octahedral crystalline form, can be prepared by a variety of techniques, for example single-jet, double-jet (including continuous removal techniques), accelerated flow rate and interrupted precipitation techniques known in the photographic art. Double-jet accelerated flow rate precipitation techniques are preferred for forming monodispersed emulsions.
  • Sensitizing compounds such as compounds of copper, thallium, cadmium, rhodium, tungsten, thorium, iridium and mixtures thereof, can be present during precipitation of the silver halide emulsion.
  • the silver halide emulsions also comprise a binder.
  • concentration of binder varies widely, but generally is within the range of about 20 to about 250 grams per mole of silver halide, preferably about 50 to about 100 grams per mole of silver halide.
  • the binder comprises a hydrophilic colloid.
  • hydrophilic colloids include naturally occurring materials such as proteins, protein derivatives, cellulose derivatives such as cellulose esters, gelatin such as alkali-treated gelatin or acid-treated gelatin, gelatin derivatives such as acetylated gelatin, phthalated gelatin and the like, polysaccharides such as dextran, gum arabic, zein, casein, pectin, collagen derivatives, collodion, agar-agar, arrowroot, albumin and the like.
  • the binder optionally comprises hydrophobic colloid and synthetic polymeric materials which are hydrophilic or water-insoluble or only slightly water-soluble, such as a polymeric latex. Such materials are useful as supplemental grain peptizers and carriers.
  • the synthetic polymeric materials preferably comprise about 20 to about 80 percent by weight of the binder.
  • Useful synthetic polymeric materials are selected from, for example, poly(vinyl lactams), acrylamide polymers, polyvinyl alcohol and its derivatives, polyvinyl acetyls, polymers of alkyl and sulfoalkyl acrylates and methacrylates, hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine, acrylic acid polymers, maleic anhydride copolymers, polyakylene oxides, methacrylamide copolymers, polyvinyl oxazolidinones, maleic acid copolymers, vinylamine copolymers, methacrylic acid copolymers, acryloyloxyalkylsulfonic acid copolymers, sulfoalkylacrylamide copolymers, polyalkyleneimine copolymers, polyamides, N,N-dialkylaminoalkyl acrylates, vinyl imidazole copolymers, vinyl sulfide copolymers,
  • Addenda known to be useful in photographic silver halide emulsions are useful in the photographic silver halide emulsion layers. Such addenda are described in, for example, Research Disclosure, December 1978, Item 17643, published by Kenneth Mason Publications, Ltd., The Old Harbourmaster's, 8 North Street, Emsworth, Hampshire P0107DD, England; Canadian Patent 1,146,001, and U.S. Patent 4,269,929.
  • the photosensitive silver halide grains need not be chemically sensitized; however, the advantages of the invention are emphasized when chemically sensitized photosensitive silver halide grains are present in the photographic element.
  • the photographic silver halide can be chemically sensitized by means of methods and compounds known in the photographic art. Such methods and compounds are described in, for example, Research Disclosure, December 1978, Item 17643 and Canadian Patent 1,146,001.
  • the silver halide emulsions can be spectrally sensitized.
  • the nucleation development control agents are useful in any location during processing in the photographic element which enables the nucleation development control agent to be in reactive association with the photosensitive silver halide grains thereby enabling increased image discrimination and reduced image development spread.
  • the nucleation development control agent can be in the silver halide emulsion layer, and/or in any other adjacent layer, such as an overcoat layer, emulsion layer, interlayer or undercoat layer, which enables the nucleation development control agent to be in such reactive association.
  • a preferred location of the nucleation development control agent is in the developer solution; however, when the nucleation development control agent is in the photographic element prior to processing, it is preferably in a layer contiguous to the silver halide emulsion layer in order to insure that the nucleation development control agent does not adversely affect the sensitometric properties of the silver halide emulsion layer.
  • the nucleation development control agent can be in the photographic element and/or a developer solution for processing the photographic element.
  • the nucleation development control agent is present in the developer solution and/or in the photographic element in any concentration which is sufficient to increase image discrimination and reduce image development spread beyond unexposed silver halide grains in close proximity to exposed silver halide grains, as described.
  • This concentration is typically within the range of 1 x 10 -4 to 3 x 10 -1 moles of nucleation development control agent per liter of development when the nucleation development control agent is in the developer, preferably with the range of 1 x 10 -3 to 3 x 10 moles per liter.
  • the concentration of nucleation development control agent is typically within the range of 1 x 10 -4 to 1 x 10 -1 moles of nucleation development control agent per mole of silver when the nucleation development control agent is present in the element, preferably 1 x 10 -4 to 1 x 10 -1 moles per mole of silver.
  • An optimum concentration of nucleation development control agent can be selected depending upon such factors as the particular nucleation development control agent, the particular developer composition, the processing conditions, particular silver halide, other components in the photographic element, desired image and location of the nucleation development control agent in the element and/or in the developer.
  • a preferred photographic element comprises a nucleating agent which is a hydrazine nucleating agent as described in Canadian Patent 1,146,001.
  • a nucleating agent which is a hydrazine nucleating agent as described in Canadian Patent 1,146,001.
  • An example of such a hydrazine nucleating agent is represented by the formula: wherein R 1 is a phenyl nucleus having a Hammett sigma value-derived electron withdrawing characteristic of less than +0.30. Hammett sigma values are known in the organic compound art, such as described in Research Disclosure, October 1974, Item 12617 and Canadian Patent 1,146,001.
  • R 1 can take the form of a phenyl nucleus which is either electron donating (electropositive) or electron withdrawing (electronegative); however, phenyl nuclei which are highly electron withdrawing produce inferior nucleating agents.
  • the electron withdrawing or electron donating characteristic of a specific phenyl nucleus can be assessed by reference to Hammett sigma values.
  • the phenyl nucleus can be assigned a Hammett sigma value-derived electron withdrawing characteristic which is the algebraic sum of the Hammett sigma values of its substituents (i.e., those of the substituents, if any, to the phenyl group).
  • the Hammett sigma values of any substituents to the phenyl ring of the phenyl nucleus can be determined algebraically simply by determining from the literature the known Hammett sigma values for each substituent and obtaining the algebraic sum thereof. Electron withdrawing substituents are assigned negative sigma values.
  • R can be a phenyl group which is unsubstituted.
  • the hydrogen atoms attached to the phenyl ring each have a Hammett sigma value of 0 by definition.
  • the phenyl nuclei can include halogen ring substituents.
  • ortho- or para-chloro or fluoro substituted phenyl groups are specifically contemplated, although the chloro and fluoro groups are each mildly electron withdrawing.
  • Preferred phenyl group substituents are those which are not electron withdrawing.
  • the phenyl groups can be substituted with straight or branched chain alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, tert-octyl, n-decyl and n-dodecyl.
  • the phenyl groups can be substituted with alkoxy groups wherein the alkyl moieties thereof can be chosen from among the alkyl groups described above.
  • the phenyl groups can also be substituted with acylamino groups.
  • Illustrative acylamino groups include acetylamino, propanoylamino, butanoylamino, octanoylamino and benzoylamino.
  • the alkyl, alkoxy and/or acylamino groups are in turn substituted with a conventional photographic ballast group, such as the ballasting moieties of incorporated couplers and other immobile photographic emulsion addenda.
  • the ballast groups typically contain at least eight carbon atoms and can be selected from both aliphatic and aromatic relatively unreactive groups, such as alkyl, alkoxy, phenyl, alkylphenyl, phenoxy, alkylphenoxy and similar groups.
  • the alkyl and alkoxy groups, including ballasting groups, if any, preferably contain from 1 to 20 carbon atoms, and the acylamino groups, including ballasting groups, if any, preferably contain from 2 to 21 carbon atoms. Generally, up to about 30 or more carbon atoms in these groups are contemplated in their ballasted form. Methoxyphenyl, tolyl, such as p-tolyl and m-tolyl, and ballasted butyramido- phenyl nuclei are specifically preferred.
  • hydrazine nucleating agents contain a formyl moiety
  • hydrazine compounds containing a benzoyl moiety which is substituted with a highly electron withdrawing substituent, such as a cyano group, are operative.
  • Such compounds have, however, been found to be inferior to the hydrazine compounds containing a formyl moiety.
  • the hydrazine nucleating agent or combination of such agents are present in the photographic element in any concentration which enables nucleation development without adversely affecting the image, for example, in a concentration of from about 10 -4 to about 10 -1 mole per mole of silver.
  • a preferred quantity of the hydrazine compound is from 5 x 10 -4 to about 5 x 10 2 mole per mole of silver.
  • Optimum results are obtained when the hydrazine nucleating agent or combination of such agents are present in a concentration of from about 8 x 10 -4 to about 5 x 10 -3 mole per mole of silver.
  • the hydrazine nucleating agent can be incorporated in a silver halide emulsion used in forming the photographic element.
  • the hydrazine compound can be present in a hydrophilic colloid layer of the photographic element, preferably a hydrophilic colloid layer which is coated to be contiguously adjacent to the emulsion layer in which the effects of the hydrazine nucleating agent are desired.
  • the hydrazine nucleating agent can, of course, be present in the photographic element distributed between or among emulsion and hydrophilic colloid layers, such as undercoating layers, interlayers, and overcoating layers.
  • the layers of the photographic element can be coated on any support that is useful in the photographic art.
  • the photographic elements can be imagewise exposed with various forms of energy that enable formation of a developable image in the photographic silver halide Exposures can be monochromatic, orthochromatic or panchromatic.
  • the photographic silver halide contained in the photographic elements can be processed following exposure to form a visible image by associating the silver halide with an aqueous alkaline medium in the presence of a developing agent contained in the medium and/or the element. Processing formulations and techniques are known in the photographic art.
  • the photographic elements can be processed in conventional developers or specialized developers conventionally employed in conjunction with lith photographic elements to obtain very high contrast images provided that the nucleation development control agent is present in the developer and/or the photographic element.
  • the elements can be processed in an activator, which can be identical to the developer in composition, but lacking a developing agent.
  • Very high contrast images can be obtained at pH values in the range of from 11 to 12.3, preferably 11.3 to 12.0. Higher pH levels can, of course, also be used, although storage stability of the developer is reduced.
  • any conventional developer composition can be employed.
  • the photographic elements can, of course, be processed with conventional developers for lith photographic elements, as illustrated by Masseth U.S. Patent 3,573,914 and VanReusel U.K. Patent 1,376,600.
  • the developers are typically aqueous solutions, although organic solvents, such as diethylene glycol, can also be included to facilitate the solvency of organic components.
  • the developers contain one or a combination of conventional developing agents, such as a polyhydroxybenzene, aminophenol, ara-phenylenediamine, ascorbic acid, pyrazolidone, pyrazolone, pyrimidine, dithionite, hydroxylamine or other conventional developing agents. It is preferred to employ hydroquinone and 3-pyrazolidone developing agents in combination.
  • the pH of the developers can be adjusted with alkali metal hydroxides and carbonates, phosphates, borax and other basic salts. To reduce gelatin swelling during development, compounds such as sodium sulfate can be incorporated into the developer. Also, compounds such as sodium thiocyanate can be present to reduce granularity. Also, chelating and sequestering agents, such as ethylenediaminetetraacetic acid or its sodium salt, can be present.
  • the nucleation development control agent is useful in any silver halide developer solution useful for nucleation development of an exposed photographic silver halide element.
  • An example of a preferred developer solution in which a nucleation development control agent is useful is described in U.S. Patent 4,269,929.
  • a useful developer solution is, for example,
  • Such a developer comprises, at a pH of 10 to 12, a dihydroxybenzene silver halide developing agent, a 3-pyrazolidone silver halide developing agent, a sulfite preservative, a contrast promoting amount of an amino compound, and an effective concentration of a water-soluble nucleation development control agent according to the invention.
  • a developer is particularly useful as a lith developer, that is a developer that is particularly useful in providing high contrast black-and-white silver images in a black-and-white photographic silver halide element ) designed to produce high contrast silver images.
  • Such developers are useful with various photographic silver halide emulsions, including high contrast silver chloride emulsions and/or other types of photographic silver halide emulsions, such as silver 5 bromoiodide emulsions.
  • a developer solution comprising a nucleation development control agent can also contain addenda known in the photographic art to be useful in photographic developer solutions.
  • the developer solution can contain solvents, buffers, sequestering agents, development accelerators, agents which reduce swell- ing of emulsion layers, hardeners, and the like.
  • a highly preferred process of high contrast development of an exposed photographic silver halide element as described comprises the step of:
  • Processing is carried out by means of manual processing or an automatic processor, such as a deep tank roller transport processor known in the photographic art.
  • Processing temperature can be ambient or elevated, for example, a temperature within the range of about 19°C to about 43°C.
  • a photographic film was prepared comprised of a poly(ethylene terephthalate) film support having coated thereon a silver bromoiodide gelatino emulsion (97.5 mole % silver bromide, 2.5 mole % silver iodide; coated at 43.1 mg of Ag/dm 2 and 26.9 mg gelatin/dm 2 ).
  • the silver bromoiodide gelatino emulsion was chemically sensitized by means of sulfur and gold compounds and spectrally sensitized by means of a spectral sensitizing dye to provide ortho spectral sensitivity.
  • the following addenda were mixed with the emulsion prior to coating:
  • Strips of the resulting photographic film were imagewise exposed to light through a sensitometric continuous wedge and a screened test object by means of a white light tungsten light source to provide a developable latent image in the photographic film. Following the imagewise exposure step, the film strips were then developed for two minutes, with continuous agitation, at 32.2°C in an aqueous developer containing the following components:
  • the dot quality values were based on a scale of 1 to 10 wherein 1 was unacceptably poor quality and 10 is excellent quality.
  • Example 2 The procedure described in Example 1 was repeated with the exception that an ortho spectrally sensitized but chemically unsensitized photographic silver chlorobromide gelatino emulsion (20 mole % AgCl and 80 mole % AgBr) which was doped by means of K 3 IrBr 6 and subsequently doctored with 11 potassium iodide per silver mole was used in place of the photographic silver bromoiodide gelatino emulsion of Example 1. The exposed photographic film strips were developed for one minute at 32.2°C. The results are summarized in following Table II.
  • a photographic silver halide film was prepared as follows:
  • Example 3 The results of Example 3 are given in following Table III:
  • a photographic film was prepared as follows:
  • the resulting photographic film was sensitometrically exposed to light to produce a developable latent image in the film.
  • the exposed film was then developed for two minutes at 32.2°C in a developer composition identical to that described in Example 1, except that the developer contained 1.41 x 10 -2 M liter of the compounds listed in column A in following Table IV:
  • the relative speed obtained by development for one minute with the control developer was arbitrarily set at 100. This value was used as a reference to determine the relative speed obtained with the modified developer.
  • the addition of Compound C-4 produced a loss in speed (sensitivity); however, the lower speed for the film containing Compound C -4 was not considered unsatisfactory in light of the fact the film speed remained basically constant even though development time was significantly changed in the series of tests.
  • the maximum density, minimum density and dot quality remained basically constant for the film containing Compound C -4 which illustrates the excellent nucleation development control which a nucleation development control agent according to the invention provides.
  • the control film in Table V has unsatisfactory minimum density at each development time.
  • Example 6 the film was the same as Example 1 and the developer (containing Compound C -4 ) was the same as Example 6 with the exception that the concentration of the 2-diethylaminoethanol was reduced from 20 to 10 ml/liter.
  • Table VI indicates that the developed image line width is significantly less for the films developed in the developer composition containing Compound C-4 compared to the developed image line width for the control.
  • Example 2 The procedure described in Example 1 was repeated with the exceptions that the developer contained one of the compounds listed in following Table VII added at 2.35 x 10- 2 moles/liter. The liated compounds were individually added. Also, the photographic film was the same as in Example 4.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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EP86117268A 1985-12-19 1986-12-11 Agent de contrôle pour le développement de germes dans des matériaux et procédés photographiques Withdrawn EP0226184A3 (fr)

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US81103385A 1985-12-19 1985-12-19
US811033 1985-12-19

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0330608A2 (fr) * 1988-02-12 1989-08-30 ILFORD Limited Procédé de développement d'un matériau pour épreuve photographique
EP0398750A2 (fr) * 1989-05-18 1990-11-22 Eastman Kodak Company Composés contrôlant le ton d'image
US5126227A (en) * 1990-10-17 1992-06-30 Eastman Kodak Company High contrast photographic elements containing ballasted hydrophobic isothioureas
EP0523464A1 (fr) * 1991-07-15 1993-01-20 Minnesota Mining And Manufacturing Company Emulsion à l'halogénure d'argent comprenant des grains ayant une structure en forme de cratère ou d'entonnoir et procédé de fabrication d'une telle émulsion
US5196292A (en) * 1991-10-17 1993-03-23 Eastman Kodak Company Nucleated high contrast photographic elements containing ballasted thioether isothioureas to inhibit pepper fog and restrain image spread
US5232818A (en) * 1991-07-25 1993-08-03 Eastman Kodak Company Nucleated high contrast photographic elements containing thioether compounds to inhibit pepper fog and restrain image spread

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2634666A1 (de) * 1975-08-02 1977-02-17 Konishiroku Photo Ind Lichtempfindliches photographisches silberhalogenid-aufzeichungsmaterial fuer die schwarz/weiss-photographie und verfahren zur herstellung hochkontrastreicher silberbilder unter verwendung des betreffenden aufzeichnungsmaterials
DE3203661A1 (de) * 1981-02-03 1982-09-16 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur bildung eines photographischen bildes
EP0032456B1 (fr) * 1980-01-14 1983-02-02 EASTMAN KODAK COMPANY (a New Jersey corporation) Procédé pour le développement de matériaux photographiques à haut contraste

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2634666A1 (de) * 1975-08-02 1977-02-17 Konishiroku Photo Ind Lichtempfindliches photographisches silberhalogenid-aufzeichungsmaterial fuer die schwarz/weiss-photographie und verfahren zur herstellung hochkontrastreicher silberbilder unter verwendung des betreffenden aufzeichnungsmaterials
EP0032456B1 (fr) * 1980-01-14 1983-02-02 EASTMAN KODAK COMPANY (a New Jersey corporation) Procédé pour le développement de matériaux photographiques à haut contraste
DE3203661A1 (de) * 1981-02-03 1982-09-16 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur bildung eines photographischen bildes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0330608A2 (fr) * 1988-02-12 1989-08-30 ILFORD Limited Procédé de développement d'un matériau pour épreuve photographique
EP0330608A3 (fr) * 1988-02-12 1990-07-18 ILFORD Limited Procédé de développement d'un matériau pour épreuve photographique
EP0398750A2 (fr) * 1989-05-18 1990-11-22 Eastman Kodak Company Composés contrôlant le ton d'image
EP0398750A3 (fr) * 1989-05-18 1992-03-18 Eastman Kodak Company Composés contrôlant le ton d'image
US5126227A (en) * 1990-10-17 1992-06-30 Eastman Kodak Company High contrast photographic elements containing ballasted hydrophobic isothioureas
EP0523464A1 (fr) * 1991-07-15 1993-01-20 Minnesota Mining And Manufacturing Company Emulsion à l'halogénure d'argent comprenant des grains ayant une structure en forme de cratère ou d'entonnoir et procédé de fabrication d'une telle émulsion
US5232818A (en) * 1991-07-25 1993-08-03 Eastman Kodak Company Nucleated high contrast photographic elements containing thioether compounds to inhibit pepper fog and restrain image spread
US5196292A (en) * 1991-10-17 1993-03-23 Eastman Kodak Company Nucleated high contrast photographic elements containing ballasted thioether isothioureas to inhibit pepper fog and restrain image spread

Also Published As

Publication number Publication date
JPS62157025A (ja) 1987-07-13
EP0226184A3 (fr) 1988-11-09

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