EP0866368A2 - Matériau d'enregistrement photographique en couleurs à haute sensibilité avec une sensibilité accrue dans la région spectrale verte - Google Patents

Matériau d'enregistrement photographique en couleurs à haute sensibilité avec une sensibilité accrue dans la région spectrale verte Download PDF

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Publication number
EP0866368A2
EP0866368A2 EP98103847A EP98103847A EP0866368A2 EP 0866368 A2 EP0866368 A2 EP 0866368A2 EP 98103847 A EP98103847 A EP 98103847A EP 98103847 A EP98103847 A EP 98103847A EP 0866368 A2 EP0866368 A2 EP 0866368A2
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EP
European Patent Office
Prior art keywords
sensitive
green
silver halide
layer
sensitization
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.)
Granted
Application number
EP98103847A
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German (de)
English (en)
Other versions
EP0866368A3 (fr
EP0866368B1 (fr
Inventor
Joerg Dr. Siegel
Hans-Ulrich Dr. Borst
Peter Dr. Bell
Ralf Dr. Büscher
Heinz Dr. Reif
Juergen Dr. Jung
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.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert AG
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Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0866368A2 publication Critical patent/EP0866368A2/fr
Publication of EP0866368A3 publication Critical patent/EP0866368A3/fr
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Publication of EP0866368B1 publication Critical patent/EP0866368B1/fr
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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
    • 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
    • G03C5/02—Sensitometric processes, e.g. determining sensitivity, colour sensitivity, gradation, graininess, density; Making sensitometric wedges

Definitions

  • the invention relates to a color photographic recording material by a special Sensitization an increased sensitivity to light from the green spectral range having.
  • the green-sensitive layer package is usually used in color negative films (CN film) sensitized so that the sensitization maximum is about 550 nm and the flanks the sensitization band towards shorter and longer wavelengths i.e. in Direction drop steeply towards both the blue and the red spectral range.
  • CN film color negative films
  • the Sensitization curve of a typical CN film is shown in FIG. 1. To this In this way, good color separation and high brilliance of the CN film are achieved.
  • EP-A-0 409 019 e.g. a color photographic recording material with described improved color rendering, which is achieved in that, for example both the green sensitive and red sensitive silver halide emulsion layers by using one or more so-called gap sensitizing dyes additional sensitization to light from the gap between two neighboring main spectral ranges, in the present case between green and red (580 up to 620 nm).
  • This will make the adjacent spectral sensitivity curves raised in the area of the secondary spectral sensitivity (gap), so that at Exposure in this area at most 0.6 logarithmic exposure units more are required to have the same color density as in the area of the adjacent main spectral sensitivity to create.
  • the sensitivity of the green-sensitive layer package can be increased without disadvantages for the color rendering in that the sensitization band in the area of the main spectral absorption green (510 to 580 nm) in all sub-layers of the green-sensitive layer package symmetrically, i.e. towards both larger and smaller wavelengths is broadened.
  • the sensitization band does not become as wide as possible in order to avoid excessive overlap of adjacent sensitization bands. It is therefore beneficial for the color rendering quality if the width of the sensitization band does not exceed the following values: b 80 70 nm b 50 95 nm b 20 140 nm.
  • the setting of the sensitization band characterized according to the invention is achieved, for example, by starting with the sensitization of the layers in question from a mixture of sensitizing dyes, at least one of which has a sensitization maximum in the range of the main spectral sensitivity, while one or more other sensitizing dyes of the mixture have a sensitization maximum, which is shifted slightly towards shorter and / or longer wavelengths compared to the sensitization maximum of the first-mentioned sensitizing dye, and that the proportion of the latter sensitizing dyes in the mixture is increased accordingly.
  • a common green sensitizing dye Green
  • a sensitizing dye with a short-wavelength shifted sensitization maximum Short green
  • a sensitizing dye with a long-wavelength shifted sensitization maximum Long green
  • the proportion of the latter dyes in the mixture can be increased accordingly in order to set a sensitization band broadened according to the invention.
  • the same measure will expediently be used for all sub-layers of the green-sensitive silver halide emulsion layer unit, even if the dyes and / used in the various sub-layers or their mixing ratios do not need to match.
  • the silver halide emulsions are sensitized in the usual way.
  • the Sensitizing dyes can be mixed simultaneously or individually in succession Silver halide emulsion can be added. The addition of one or more sensitizing dyes already during the grain growth phase and / or during the chemical ripening is possible.
  • a sensitization band results in all of their sub-layers, which is characterized by the following parameters: 635 nm ⁇ ⁇ (p Max ) ⁇ 660 nm 70 nm ⁇ b 80 ⁇ 35 nm 95 nm ⁇ b 50 ⁇ 56 nm 145 nm ⁇ b 20th ⁇ 96 nm.
  • the following parameters apply to the partial layers of the red-sensitive silver halide emulsion layer: b 80 ⁇ 49 nm, and preferably b 80 ⁇ 65 nm b 50 ⁇ 71 nm, and preferably b 80 ⁇ 89 nm b 20th ⁇ 111 nm, and preferably b 80 ⁇ 130 nm.
  • color photographic recording materials are in particular Color negative films and color reversal films.
  • An overview of typical color photography Materials as well as preferred embodiments and processing processes can be found in Research Disclosure 37038 (February 1995).
  • the photographic materials consist of a support on which at least one photosensitive Silver halide emulsion layer is applied.
  • An overview of carrier materials and on the front and back of the auxiliary layers applied is in Research Disclosure 37254, Part 1 (1995), p. 285.
  • the color photographic materials usually contain at least one each red sensitive, green sensitive and blue sensitive silver halide emulsion layer and optionally intermediate layers and protective layers.
  • Color photographic films such as color negative films and color reversal films show in the the following sequence on the carrier 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers on the layers of the same spectral Sensitivity differ in their photographic sensitivity, with the less sensitive sub-layers are usually arranged closer to the support than the more sensitive sub-layers.
  • Deviations in the number and arrangement of the light-sensitive layers can lead to Achieve certain results.
  • all can be highly sensitive Layers to form a layer package and all low-sensitivity layers another layer package can be summarized in a photographic film in order to Increase sensitivity (DE-A-25 30 645).
  • Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.
  • Photographic materials with camera sensitivity usually contain silver bromoiodide emulsions, which may also contain small amounts of silver chloride can.
  • Photographic copying materials contain either silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.
  • the maximum Absorption of those formed from the couplers and the color developer oxidation product Dyes are preferably in the following ranges: yellow coupler 430 to 460 nm, Magenta couplers 540 to 560 nm, cyan couplers 630 to 700 nm.
  • the color couplers are the relevant silver halide emulsion layer units or their sub-layers spatially and spectrally assigned.
  • Spatial assignment is understood to mean that the color coupler is in one such a spatial relationship to the silver halide layer in question that an interaction between them is possible, which is a pictorial match between the silver image formed during development and that from the color coupler color image generated. This is usually achieved by the color coupler in the silver halide emulsion layer itself or in an adjacent one possibly non-photosensitive binder layer.
  • Spectral assignment means that the spectral sensitivity of the relevant light sensitive silver halide emulsion and the color of the from the spatially assigned color couplers generated partial color image in a certain Are related to each other, the spectral sensitivity of each Color separation (red, green, blue) a complementary colored partial color image (cyan, magenta, Yellow) is assigned.
  • Color photographic films are used to improve sensitivity, graininess, Sharpness and color separation are often used when reacting with the compounds Developer oxidation product release compounds that are photographically active, e.g. DIR couplers that release a development inhibitor.
  • the mostly hydrophobic color coupler, but also other hydrophobic components of the Layers are usually dissolved in high-boiling organic solvents or dispersed. These solutions or dispersions are then in an aqueous Binder solution (usually gelatin solution) emulsifies and lie after drying of the layers as fine droplets (0.05 to 0.8 mm diameter) in the layers in front.
  • aqueous Binder solution usually gelatin solution
  • Suitable high-boiling organic solvents, methods for incorporation into the Layers of photographic material and other methods, chemical compounds to be incorporated into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.
  • the usually arranged between layers of different spectral sensitivity non-light-sensitive intermediate layers can contain agents that have a unwanted diffusion of developer oxidation products from a photosensitive in another light-sensitive layer with different spectral sensitization prevent.
  • Suitable connections can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and in Research Disclosure 37038, Part III (1995), p. 84.
  • the photographic material can also contain UV light absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve the stability of dyes, couplers and whites as well as to reduce the color fog, plasticizers (latices), biocides and other included.
  • Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292 and in Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff.
  • the layers of color photographic materials are usually hardened, i.e. that Binder used, preferably gelatin, is replaced by suitable chemical Process networked.
  • Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and in Research Disclosure 37038, Part XII (1995), page 86.
  • a color photographic recording material for color negative color development was produced (layer structure 1 - comparison) by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application. All silver halide emulsions were stabilized per 1 mol AgNO 3 with 0.5 g 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • Layer 1 (antihalo layer) black colloidal silver sol with
  • Sensitizing dyes used in layer structure 1 are Sensitizing dyes used in layer structure 1:
  • the material After exposing a gray wedge, the material is processed using a color negative development process, which is carried out in The British Journal of Photography ", 1974, pages 597 and 198.
  • the sensitivity maximum and the width of the sensitivity distribution [green] at 80%, 50% and 20%, based on the maximum intensity of the sensitization band are also used (b 80 , b 50 , b 20 ).
  • Table 1 also shows the corresponding values (b 80 , b 50 , b 20 and the increase in sensitivity achieved) for the layer structures 2 to 6 described in the examples below.
  • CIELAB measurements are usually used for the colorimetric description of CN films.
  • the method is detailed, for example in RWG Hunt The Reproduction of Color ⁇ ", Fountain Press (1988).
  • the color reproduction is characterized with the help of the luminance L and the chromaticity constants a and b.
  • color distances ⁇ E can be determined, the statements about a change in the color saturation or the Experience has shown that a shift of 3 to 5 ⁇ E units is perceptible to the human eye.
  • Table 2 shows the colorimetric characterization for layer structure 1 (comparison film) and in FIG. 3 the graphical representation of the chromaticity constants a and b specified.
  • the spectral sensitization of the green-sensitive layer package was carried out as follows: layer dyes used Mixing ratio 6 XGS-1, XGS-2, XGS-3 2.6: 1: 0.9 7 XGS-1, XGS-2, XGS-3 2.5: 1: 0.8
  • the description of the sensitivity distribution (Table 1, Fig. 4) shows the symmetrical Broadening of the sensitization band, especially in the area of the main spectral sensitivity.
  • the spectral sensitization of the green-sensitive layer package was carried out as follows: layer dyes used Mixing ratio 6 XGS-6, XGS-5, XGS-3 2.1: 1.0: 1.1 7 XGS-6, XGS-5, XGS-3 2.2: 1.0: 1.0
  • Table 1 The description of the sensitivity distribution (Table 1) shows the symmetrical one Broadening of the awareness fire, especially in the area of main spectral sensitivity.
  • the spectral sensitization of the green-sensitive layer package was carried out as follows: layer dyes used Mixing ratio 6 XGS-7, XGS-5, XGS-3 2.2: 1.0: 1.5 7 XGS-7, XGS-5, XGS-3 2.3: 1.0: 1.6
  • the description of the sensitivity distribution (Table 1) shows the symmetrical one Broadening of the sensitization band, especially in the area of the main spectral sensitivity.
  • the spectral sensitization of the green-sensitive layer package was carried out as follows: layer dyes used Mixing ratio 6 XGS-7, XGS-2, XGS-3 2.0: 1.0: 1.5 7 XGS-7, XGS-2, XGS-3 2.1: 1.0: 1.4
  • the description of the sensitivity distribution (Table 1) shows the symmetrical one Broadening of the sensitization band, especially in the area of the main spectral sensitivity.
  • the spectral sensitization of the green-sensitive layer package was carried out as follows: layer dyes used Mixing ratio 6 XGS-1, XGS-4, XGS-3 1.6: 1.4: 1.6 7 XGS-1, XGS-4, XGS-3 1.6: 1.4: 1.6
  • the description of the sensitivity distribution (Table 1) shows the symmetrical one Broadening of the sensitization band, especially in the area of the main spectral sensitivity.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photoreceptors In Electrophotography (AREA)
EP98103847A 1997-03-18 1998-03-05 Matériau d'enregistrement photographique en couleurs à haute sensibilité avec une sensibilité accrue dans la région spectrale verte Expired - Lifetime EP0866368B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19711144A DE19711144A1 (de) 1997-03-18 1997-03-18 Hochempfindliches farbfotografisches Aufzeichnungsmaterial mit erhöhter Empfindlichkeit im grünen Spektralbereich
DE19711144 1997-03-18

Publications (3)

Publication Number Publication Date
EP0866368A2 true EP0866368A2 (fr) 1998-09-23
EP0866368A3 EP0866368A3 (fr) 1998-10-07
EP0866368B1 EP0866368B1 (fr) 2003-11-12

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EP98103847A Expired - Lifetime EP0866368B1 (fr) 1997-03-18 1998-03-05 Matériau d'enregistrement photographique en couleurs à haute sensibilité avec une sensibilité accrue dans la région spectrale verte

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EP (1) EP0866368B1 (fr)
JP (1) JPH10268487A (fr)
DE (2) DE19711144A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6093526A (en) * 1999-03-01 2000-07-25 Eastman Kodak Company Photographic film element containing an emulsion with broadened green responsivity
US6296994B1 (en) 1999-03-01 2001-10-02 Eastman Kodak Company Photographic elements for colorimetrically accurate recording intended for scanning

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1914292A1 (de) * 1968-03-21 1969-10-09 Eastman Kodak Co Photographisches Aufzeichnungsmaterial
EP0409019A2 (fr) * 1989-07-20 1991-01-23 Agfa-Gevaert AG Matériau d'enregistrement photographique en couleurs au rendu chromatique amélioré
US5037728A (en) * 1987-09-11 1991-08-06 Fuji Photo Film Co., Ltd. Photographic material package unit
EP0677782A1 (fr) * 1994-04-15 1995-10-18 Eastman Kodak Company Elément photographique comprenant une émulsion avec sensibilité particulière au bleu et méthode de traitement de celui-ci

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1914292A1 (de) * 1968-03-21 1969-10-09 Eastman Kodak Co Photographisches Aufzeichnungsmaterial
US5037728A (en) * 1987-09-11 1991-08-06 Fuji Photo Film Co., Ltd. Photographic material package unit
EP0409019A2 (fr) * 1989-07-20 1991-01-23 Agfa-Gevaert AG Matériau d'enregistrement photographique en couleurs au rendu chromatique amélioré
EP0677782A1 (fr) * 1994-04-15 1995-10-18 Eastman Kodak Company Elément photographique comprenant une émulsion avec sensibilité particulière au bleu et méthode de traitement de celui-ci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6093526A (en) * 1999-03-01 2000-07-25 Eastman Kodak Company Photographic film element containing an emulsion with broadened green responsivity
US6296994B1 (en) 1999-03-01 2001-10-02 Eastman Kodak Company Photographic elements for colorimetrically accurate recording intended for scanning

Also Published As

Publication number Publication date
EP0866368A3 (fr) 1998-10-07
EP0866368B1 (fr) 2003-11-12
DE59810120D1 (de) 2003-12-18
JPH10268487A (ja) 1998-10-09
DE19711144A1 (de) 1998-09-24

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