EP0514450B1 - Materiau a enregistrement photographique muni d'une couche absorbante destinee a reduire la vitesse photographique - Google Patents

Materiau a enregistrement photographique muni d'une couche absorbante destinee a reduire la vitesse photographique Download PDF

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Publication number
EP0514450B1
EP0514450B1 EP91904108A EP91904108A EP0514450B1 EP 0514450 B1 EP0514450 B1 EP 0514450B1 EP 91904108 A EP91904108 A EP 91904108A EP 91904108 A EP91904108 A EP 91904108A EP 0514450 B1 EP0514450 B1 EP 0514450B1
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EP
European Patent Office
Prior art keywords
silver halide
absorbing layer
photographic
radiation
transition metal
Prior art date
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.)
Expired - Lifetime
Application number
EP91904108A
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German (de)
English (en)
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EP0514450A1 (fr
Inventor
Anthony D. Gingello
Richard David Lucitte
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
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Eastman Kodak Co
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Publication date
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • 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
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/8255—Silver or silver compounds therefor

Definitions

  • the present invention relates to a photographic recording material and more particularly to a photographic recording material which contains an absorbing layer.
  • Absorbing layers are known in the photographic art. They are used selectively to screen undesired radiation from coming into contact with one or more underlying photosensitive layers. For example, colloidal silver layers are used between blue sensitive and green sensitive layers in color photographic recording materials in order to prevent unwanted blue light from reaching underlying green and red sensitized layers.
  • a colloidal silver layer is also known to be used on a photographic recording material as an overcoat layer in order to correct color reproduction. Where colloidal silver layers are used they are generally removed from the photographic material during processing by first being converted into silver halide in a bleaching step and then being dissolved and removed in a fixing bath.
  • U. S. Patent 4,052,215 describes the use of soluble iodide compounds in non-light sensitive colloidal silver filter layers in order to reduce formation of contact fog in photographic recording materials. This technique has the drawback of also requiring a bleaching step to convert colloidal silver to silver halide for subsequent removal during photographic processing.
  • U. S. Patent 4,818,659 proposes the use of two photosensitive silver halide layers, each having at least 80 mol % of silver chloride, for safe light protection against ultraviolet radiation.
  • the silver halide emulsion layer with greater photosensitivity is coated closer to the support and at least one of the silver halide layers requires the presence of both a hydrazine compound and a dye which has an absorption between about 400 nm and 500 nm.
  • this technique poses problems with the use of dyes. For example, dyes are relatively difficult to remove from a photographic material. Dyes tend to accumulate in and contaminate developer solutions thereby causing stain as well as developer instability problems. Also, the presence of a dye frequently causes loss of maximum density in the final image.
  • U. S. Patent 4,873,181 describes a silver halide photographic material comprising a support, a silver halide emulsion layer overlying the support, and an auxiliary layer containing non-light-sensitive silver halide grains having an average grain size of not more than 0.5 ⁇ m which can overlie the emulsion layer.
  • the purpose of the auxiliary layer is to provide high covering power, improved graininess and improved development stability.
  • a photographic element comprising (1) a support, (2) a photosensitive silver halide emulsion layer, and (3) a hydrophilic colloid radiation-absorbing layer, separate from said emulsion layer, which provides reduced photographic speed; characterized in that said radiation-absorbing layer is (A) incapable of forming therein a developable latent image and (B) comprised of desensitized silver halide grains dispersed in the hydrophilic colloid binder; said silver halide grains (a) being doped with a desensitizing amount of a transition metal coordination complex containing one or more nitrosyl or thionitrosyl ligands and a transition metal chosen from groups 5 to 10 inclusive of the simplified periodic table of elements published in "Chemical and Engineering News", p.26, February 4, 1985, (b) having a grain size of from 0.01 ⁇ m to 4 ⁇ m, and (c) being present in said radiation-absorbing layer in an amount of from 50 mg/m2 to 10 g/
  • the absorbing layer used in this invention is capable of reducing the speed of a photosensitive layer contained in a photographic recording material without causing loss of either maximum density values or desired high contrast values.
  • the absorbing layer permits safe roolight handling of photographic recording materials under lighting conditions which include fluorescent illumination, due to its absorption capability of ultraviolet radiation.
  • a preferred radiation absorbing layer is capable of absorbing radiation below a wavelength of about 530 nm, is capable of being removed during photographic processing, lends itself to silver recovery, is capable of reducing the photographic speed of the recording material and which preserves maximum density and contrast values, but which is incapable of forming therein a developable latent image.
  • the absorbing layer can be positioned on either side of the support depending upon the transparency of the support with respect to actinic radiation. Since the purpose of the absorbing layer is to impart safelight handling properties to the photographic recording material, its location within the photographic material is determined by this objective. One common position in a photographic recording material is over a photosensitive silver halide layer in the direction toward the illuminating light source.
  • the absorbing layer comprises silver halide grains of reduced photosensitivity dispersed in a hydrophilic colloid.
  • concentration of the silver halide in the absorbing layer is from about 50 mg/m2 to about 10 grams/m2 having a particle size of from 0.01 ⁇ m to about 0.4 ⁇ m.
  • the silver halide grains are present in the absorbing layer in an amount of from about 0.5 grams/m2 to about 3 grams/m2. Most preferably the grains have particle sizes between about 0.05 ⁇ m and 0.2 ⁇ m.
  • the type of silver halide used in the absorbing layer may include silver chloride, silver bromide, silver iodide or mixed silver halides such as, for example, silver chlorobromide, silver bromoiodide or silver chlorobromoiodide.
  • the silver halide grains can be of any morphology so long as the grain size is within the range of specifications noted above. While silver halides of various types can be employed, the preferred halide is silver bromide.
  • the fine grained silver halide used in the present invention can be prepared by using methods known in the art. For example, the methods described in P. Glafkides, Photographic Chemistry , Vol. 1, pp 365-368 (1958), or in Mees and James, The Theory of the Photographic Process , p 36 (1966) are useful in this respect.
  • the fine grained silver halide can be prepared by the methods as described in U.S. Patent Nos. 3,801,326 and 3,737,017. Further, the so-called Lippmann type emulsion which contains extremely fine grained silver halides (having a diameter of 0.1 micron or less) can be employed. These Lippmann emulsions can be obtained by precipitation of silver halides in the presence of a compound, for example a heterocyclic mercapto compound as described in British Patent No. 1,204,623, a heterocyclic mercapto precursor compound as described in West German Patent Application (OLS) No. 2,161,044 or compounds as described in U.S. Patent Nos. 3,661,592 and 3,704,130.
  • a compound for example a heterocyclic mercapto compound as described in British Patent No. 1,204,623, a heterocyclic mercapto precursor compound as described in West German Patent Application (OLS) No. 2,161,044 or compounds as described in U.S. Patent
  • the silver halide grains are dispersed in a hydrophilic colloid.
  • the preferred colloid is gelatin, for example, alkali treated gelatin derived from cattle bone or hide or acid treated gelatin derived from pigskin.
  • Gelatin derivatives are also useful such as acetylated gelatin and phthalated gelatin.
  • the photographic sensitivity of the absorbing layer needs to be reduced in order to eliminate therein any latent image formation. This is accomplished by densensitization of the silver halide utilizing an electron trapping compound.
  • a compound is a "dopant" which is a material other than a silver or a halide ion which is contained within the silver halide grain.
  • the dopant when utilized within the ranges noted below, causes desensitization of the silver halide thereby eliminating or minimizing latent image formation.
  • the dopants utilized in desensitizing the silver halide absorbing layer of this invention are transition metal complexes. Such dopants include both the transition metal and its ligands. Together, the ligand and the transition metal are capable of significantly desensitizing silver halide photographic emulsions.
  • the dopants contained within the silver halide grains employed in an absorbing layer of this invention are transition metal coordination complexes which contain one or more nitrosyl or thionitrosyl ligands and a transition metal chosen from groups 5 to 10 inclusive of the periodic table of elements.
  • transition metal coordination complexes which contain one or more nitrosyl or thionitrosyl ligands and a transition metal chosen from groups 5 to 10 inclusive of the periodic table of elements.
  • Such ligands are described in U.S. Patent 4,933,272 issued June 12, 1990. These ligands have the formula: where X is oxygen in the case of nitrosyl ligands and sulfur in the case of thionitrosyl ligands.
  • Preferred dopants utilized in this invention are transition metal coordination complexes having the formula: [M(NX)(L)5] n wherein: M is a ruthenium, rhenium, chromium, osmium or iridium transition metal; X is oxygen or sulfur; L is a ligand; and n is -1, -2 or -3.
  • Typical hexacoordinated transition metal complexes are shown in the table below.
  • Transition metal complexes having ligands are known to coprecipitate, at least in part, with silver halide grains.
  • concentration range for use as electron trapping agents to desensitize filter layers to be used in this invention is at least 10 ⁇ 6 mole/silver mole and preferably is between 10 ⁇ 6 and 10 ⁇ 3 mole/Ag mole.
  • the desensitized absorbing layer of this invention is capable of providing the capacity of absorbing undesirable actinic radiation between the wavelengths of about 250 nm to about 530 nm. This results in reduced photographic speed of the photosensitive layer.
  • the exact choice of silver halide usage in the absorbing layer will vary depending upon the absorption efficiency of the silver halide in the spectral region of interest.
  • Photographic recording materials comprising an absorbing layer of the present invention can be either black-white or color. In the latter, there can be a single color or a multicolor photographic material. In a multicolor material color formers known in the art can be used. For example, dye-forming color couplers can be incorporated in the recording materials in the usual manner.
  • a typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.
  • the element can contain additional layers, such as interlayers, overcoat layers, subbing layers, and the like.
  • the silver halide emulsions employed in the recording material of this invention can be comprised of silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • the emulsions can include silver halide grains of any conventional shape or size. Specifically, the emulsions can include coarse, medium or fine silver halide grains. High aspect ratio tabular grain emulsions are specifically contemplated, such as those disclosed by Wilgus et al U.S. Patent 4,434,226, Daubendiek et al U.S. Patent 4,414,310, Wey U.S.
  • Patent 4,399,215 Solberg et al U.S. Patent 4,433,048, Mignot U.S. Patent 4,386,156, Evans et al U.S. Patent 4,504,570, Maskasky U.S. Patent 4,400,463, Wey et al U.S. Patent 4,414,306, Maskasky U.S. Patents 4,435,501 and 4,643,966 and Daubendiek et al U.S. Patents 4,672,027 and 4,693,964.
  • silver bromoiodide grains with a higher molar proportion of iodide in the core of the grain than in the periphery of the grain such as those described in GB 1.027,146; JA 54/48,521; U.S. 4,379,837; U.S. 4,444,877; U.S. 4,665.012; U.S. 4,686,178; U.S. 4,565,778; U.S. 4,728,602; U.S. 4,668,614; U.S. 4,636,461; EP 264,954.
  • the silver halide emulsions can be either monodisperse or poly-disperse as precipitated.
  • the grain size distribution of the emulsions can be controlled by silver halide grain separation techniques or by blending silver halide emulsions of differing grain sizes.
  • Sensitizing compounds such as compounds of copper, thallium, lead, bismuth, cadmium and Group VIII noble metals, can be present during precipitation of the silver halide emulsion.
  • the silver halide emulsions can be surface-sensitive, i.e., emulsions that form latent images primarily on the surfaces of the silver halide grains, or internal latent image-forming emulsions, i.e., emulsions that form latent images predominantly in the interior of the silver halide grains.
  • the emulsions can be negative-working emulsions, such as surface-sensitive emulsions, or unfogged internal latent image-forming emulsions, or direct-positive emulsions of the unfogged, internal latent image-forming type, which are positive-working when development is conducted with uniform light exposure or in the presence of a nucleating agent.
  • Surface sensitization can also be accomplished using noble metals (e.g., gold), middle chalcogens (e.g., sulfur, selenium, or tellurium), and reduction sensitizers, employed individually or in combination.
  • noble metals e.g., gold
  • middle chalcogens e.g., sulfur, selenium, or tellurium
  • reduction sensitizers employed individually or in combination.
  • Typical chemical sensitizers are listed in Research Disclosure , 1978, Item 17643, cited above, Section III.
  • the silver halide emulsions can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra-, and polynuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls, and streptocyanines.
  • Illustrative spectral sensitizing dyes are disclosed in Research Disclosure , 1978, Item 17643, Section IV.
  • Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure, 1978, Item 17643, Section IX and the publications cited therein.
  • the photographic elements can be coated on a variety of supports as described in Research Disclosure, 1978, Item 17643, Section XVII and the references described therein.
  • Solutions II, III, and IV were added simultaneously at a constant rate to kettle solution I.
  • Solutions II and III concluded flow at 35 minutes, whereas solution IV terminated flow at 5 minutes.
  • Soluble salts were removed from the silver halide emulsion and gelatin was added. pH and vAg, were adjusted to 6.0 and 91 mv, respectively.
  • the resulting cubic emulsion was monodispersed with a mean grain size of .086 ⁇ m.
  • the emulsion contained 63 mg of K2Ru(NO)Br5/mole Ag, 39.6 g gelatin/mole Ag, and 43.5 moles of AgBr.
  • the photographic light sensitive material used in this invention was a cubic .15 ⁇ m monodispersed AgCl emulsion doped with 20 mg K2Ru(NO)Br5/mole silver.
  • the emulsion was prepared in a similar fashion to the absorbing layer emulsion with vAg controlled at 140 mv.
  • the AgBr absorbing layer emulsion was coated over the photographic light sensitive AgCl emulsion which was coated on a 4 mil estar support.
  • the absorbing layer emulsion was coated at varying silver laydowns, 1356 mg gel/m2, and contained both surfactants and 107 mg/m2 of the hardener bis(vinylsulfonylmethyl)-ether (BVSM).
  • the photographic light sensitive AgCl emulsion was coated at 3336 mg Ag/m2, 2722 mg gel/m2, and contained 4-hydroxy-6- methyl-2-methylmercapto-1,3,3A,7-tetraazindene, and 130 mg/m2 of BVSM.
  • Samples were exposed in contact with a type - M carbon stepwedge having increments of 0.10 density. Radiation for exposure was provided by a 500 watt iron doped metal halide lamp.
  • Halftone reproduction was accomplished by exposing a square dot pattern of 50% dot area in vacuum contact with exposures provided by an iron doped metal halide lamp.
  • Strips of the above photosensitive material were processed in KODAK RA200 Rapid Access Developer in a KODAK K65A processor for 32 seconds at 30 degrees C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

On décrit une couche absorbante conçue pour les matériaux à enregistrement photographique et servant à permettre la manipulation de ceux-ci dans une pièce dont l'éclairage comprend des radiations ultraviolettes.

Claims (6)

  1. Elément photographique comprenant (1) un support, (2) une couche d'émulsion aux halogénures d'argent photosensible, et (3) une couche de colloïde hydrophile absorbant le rayonnement, séparée de la couche d'émulsion et abaissant la rapidité photographique ;
    caractérisé en ce que
    la couche absorbant le rayonnement est
    (A) incapable de former une image latente développable, et
    (B) comprend des grains d'halogénure d'argent désensibilisés dispersés dans un liant colloïde hydrophile ; les grains d'halogénure d'argent
    (a) étant dopés avec une quantité désensibilisante d'un complexe de coordination de métal de transition contenant un ou plusieurs ligands nitrosyle ou thionitrosyle et un métal de transition choisi parmi les groupes 5 à 10 compris de la classification périodique des éléments publiée dans "Chemical and Engineering News", p 26, 4 février 1985,
    (b) ayant une taille de grains comprise entre 0,01 µm et 4 µm, et
    (c) étant présent dans la couche absorbant le rayonnement en quantité comprise entre 50 mg/m² et 10 g/m².
  2. Elément photographique selon la revendication 1, dans lequel les grains ont une taille comprise entre 0,05 µm et 0,2 µm et sont présents dans la couche absorbant le rayonnement en quantité comprise entre 0,5 g/m² et 3 g/m².
  3. Elément photographique selon la revendication 1 ou 2, dans lequel l'halogénure d'argent désensibilisé est le bromure d'argent.
  4. Elément photographique selon l'une quelconque des revendications 1 à 3, dans lequel la couche absorbant le rayonnement recouvre la couche d'émulsion aux halogénures d'argent photosensible.
  5. Elément photographique selon l'une quelconque des revendications 1 à 4, dans lequel le complexe de coordination du métal de transition a la formule

            [M(NX)(L)₅]n

    où M est le ruthénium, le rhénium, le chrome, l'osmium ou l'iridium ; X est l'oxygène ou le soufre ; L est un ligand ; et n est 1, 2, ou 3.
  6. Produit photographique selon l'une quelconque des revendications 1 à 4 dans lequel le complexe de coordination du métal de transition est K₂Ru(NO)Br₅.
EP91904108A 1990-02-06 1991-02-04 Materiau a enregistrement photographique muni d'une couche absorbante destinee a reduire la vitesse photographique Expired - Lifetime EP0514450B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US475542 1983-03-15
US47554290A 1990-02-06 1990-02-06
PCT/US1991/000680 WO1991012562A1 (fr) 1990-02-06 1991-02-04 Materiau a enregistrement photographique muni d'une couche absorbante destinee a reduire la vitesse photographique

Publications (2)

Publication Number Publication Date
EP0514450A1 EP0514450A1 (fr) 1992-11-25
EP0514450B1 true EP0514450B1 (fr) 1994-04-20

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EP91904108A Expired - Lifetime EP0514450B1 (fr) 1990-02-06 1991-02-04 Materiau a enregistrement photographique muni d'une couche absorbante destinee a reduire la vitesse photographique

Country Status (4)

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EP (1) EP0514450B1 (fr)
JP (1) JP2892832B2 (fr)
DE (1) DE69101778T2 (fr)
WO (1) WO1991012562A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252451A (en) * 1993-01-12 1993-10-12 Eastman Kodak Company Photographic emulsions containing internally and externally modified silver halide grains
US5279933A (en) * 1993-02-03 1994-01-18 Eastman Kodak Company High-contrast photographic elements with improved print-out capability
US5773206A (en) * 1997-04-21 1998-06-30 Eastman Kodak Company Infrared sensor detectable imaging elements

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2251837A1 (en) * 1973-11-16 1975-06-13 Kodak Pathe Polycontrast silver halide photographic product - with non-photo sensitive siler halide in filter layer, giving improved contrast
JPS58143335A (ja) * 1982-02-19 1983-08-25 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
US4835093A (en) * 1988-04-08 1989-05-30 Eastman Kodak Company Internally doped silver halide emulsions
US4933272A (en) * 1988-04-08 1990-06-12 Eastman Kodak Company Photographic emulsions containing internally modified silver halide grains

Also Published As

Publication number Publication date
DE69101778T2 (de) 1994-11-24
EP0514450A1 (fr) 1992-11-25
JPH05504007A (ja) 1993-06-24
JP2892832B2 (ja) 1999-05-17
WO1991012562A1 (fr) 1991-08-22
DE69101778D1 (de) 1994-05-26

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