EP0317885B1 - Papier noir et blanc à gradation variable - Google Patents

Papier noir et blanc à gradation variable Download PDF

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Publication number
EP0317885B1
EP0317885B1 EP88119073A EP88119073A EP0317885B1 EP 0317885 B1 EP0317885 B1 EP 0317885B1 EP 88119073 A EP88119073 A EP 88119073A EP 88119073 A EP88119073 A EP 88119073A EP 0317885 B1 EP0317885 B1 EP 0317885B1
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EP
European Patent Office
Prior art keywords
silver halide
alkyl
emulsion
oder
gradation
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
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EP88119073A
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German (de)
English (en)
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EP0317885A3 (en
EP0317885A2 (fr
Inventor
Helmut Dr. Kampfer
Walter Dr. Pätzold
Günther Dr. Mahlberg
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/005—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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain

Definitions

  • the invention relates to a variable-grade black-and-white paper (BW paper) which contains at least one emulsion which is sensitive in the green and blue spectral range, a larger exposure range being obtained in the green than in the blue.
  • BW paper black-and-white paper
  • Gradation-variable light-sensitive silver halide materials contain emulsions that are light-sensitive for different spectral ranges. Depending on the composition of the copying light, a harder or softer gradation is achieved. The emulsions are usually mixed before pouring so that only one layer has to be poured. There is a risk that re-sensitization occurs, ie that the sensitizing dye is desorbed from the silver halide grains of an emulsion and absorbed on grains of an unsensitized, blue-sensitive emulsion. This is undesirable, since such a differentiated exposure by changing the copying light no longer leads to the desired result leads. Under unfavorable conditions, the process of sensitization is not limited to the casting solution, but can also occur on the finished material, for example under the influence of moisture, heat or both.
  • the object of the invention was therefore to find a method in which a spectral green sensitization which does not have the disadvantages described is used to produce a gradation-variable SW paper.
  • Alkyl, sulfoalkyl, carboxyalkyl, hydroxyalkyl and acyloxyalkyl radicals have in particular 1 to 6 carbon atoms in the alkyl part.
  • Acyl is preferably understood to mean C1-C4 alkylcarbonyl.
  • Halogen is preferably chlorine.
  • Alkoxy and alkoxycarbonyl have in particular 1 to 4 carbon atoms in the alkoxy part.
  • Suitable anions are halides such as chloride and bromide, and sulfate and alkyl sulfates such as methosulfate and ethosulfate, and also perchlorate and p-toluenesulfonate.
  • the green sensitizer is added to only part of the emulsion, in particular 20 to 80% by weight.
  • the gradation-variable SW paper contains a mixture of at least one emulsion which contains at least one green sensitizer of the formula I and at least one spectrally blue (in the range from 420 to 480 ⁇ m) sensitized emulsion.
  • the amount of blue-sensitized emulsion is in particular 15 to 60% by weight. A particularly good gradation differentiation is achieved through these measures.
  • the heterocyclic rings supplemented by P are preferably pyrroline, oxazole, imidazole, thiazole, selenazole and their benzo-fused derivatives and 1,3,4-thiadiazole, which are substituted by C1-C4-alkyl, C1-C4-alkoxy, cyano, halogen, aryl, in particular phenyl, C1-C4-alkylthio, carb-C1-C4-alkoxy-C1-C4-alkylthio, carboxy-C1-C4-alkylthio, sulfo-C1-C4-alkyl and sulfoaryl, especially sulfophenyl may be substituted.
  • heterocycles supplemented by Q can be substituted by C1-C5-alkyl or aryl, in particular phenyl, where aryl can in turn be substituted, preferably by carboxy or sulfo.
  • the amount of blue sensitizer is not critical; 10 to 300 ⁇ mol / mol Ag is preferably used, in particular 20 to 150 ⁇ mol.
  • the average grain size of the silver halide grains is preferably 0.2 to 0.6 ⁇ m, preferably 0.4 to 0.5 ⁇ m.
  • the silver halide is composed in particular of 20 to 80 mol% AgBr, 80 to 20 mol% AgCl and 0 to 5 mol% AgI.
  • the silver halide crystals can be doped with Rh3+, Ir4+, Cd2+, Zn2+, Pb2+.
  • the emulsion can be desalted in the customary manner (dialysis, flocculation and redispersion, ultrafiltration).
  • the binder is an essential component of the at least one light-sensitive layer in addition to the silver halide.
  • Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
  • Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
  • Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products.
  • Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers are examples of this.
  • the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
  • functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be obtained by acidic or alkaline digestion.
  • the production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
  • the silver halide present as a light-sensitive component in the photographic material can be predominantly compact crystals, which are e.g. are regular cubic or octahedral or can have transitional forms.
  • platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably greater than 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different.
  • the grain size distribution can be both homodisperse and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate more than ⁇ 30% from the mean grain size.
  • the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • the silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
  • the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate at which just yet no new germs arise, should not be exceeded.
  • the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
  • so-called inverse precipitation with an excess of silver ions is also possible.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as Benzenesulfinic acid or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benzotriazoles or benzothiazolium salts are used.
  • metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as Benzenesulfinic acid or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benzotriazoles or benzothiazolium salts are used.
  • Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
  • these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • a water-solubilizing group for example a carboxyl group or sulfo group.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • Chemical sensitization can take place through unstable sulfur compounds (e.g. thiosulfate, diacetyl-thiourea), through gold-sulfur ripening or reduction ripening. Chemical sensitization can be carried out with the addition of Ir, Rh, Pb, Cd, Hg, Au, as well as the addition of optical sensitizers or stabilizers.
  • unstable sulfur compounds e.g. thiosulfate, diacetyl-thiourea
  • Chemical sensitization can be carried out with the addition of Ir, Rh, Pb, Cd, Hg, Au, as well as the addition of optical sensitizers or stabilizers.
  • the photographic material may further contain UV light absorbing compounds, whites, spacers, formalin scavengers and others.
  • Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film.
  • Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A 3 533 794), 4-thiazolidone compounds (US-A 3 314 794 and 3 352 681), benzopheno compounds (JP-A 2784/71), cinnamic acid ester compounds (US-A 3 705 805 and 3 707) 375), butadiene compounds (US-A 4 045 229) or benzoxazole compounds (US-A 3 700 455).
  • Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
  • ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
  • Suitable whiteners are e.g. in Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter V.
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • binders of the material according to the invention are hardened with suitable hardeners, for example with hardeners of the epoxy type, the ethyleneimine type, the acryloyl type or the vinylsulfone type.
  • suitable hardeners for example with hardeners of the epoxy type, the ethyleneimine type, the acryloyl type or the vinylsulfone type.
  • suitable hardeners for example with hardeners of the epoxy type, the ethyleneimine type, the acryloyl type or the vinylsulfone type.
  • dizine, triazine or 1,2-dihydroquinoline series hardeners are also suitable.
  • the binders of the material according to the invention are preferably hardened with instant hardeners.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that hardening is completed to the extent that no further change in the sensitometry and the Swelling of the layer structure occurs. Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
  • the materials according to the invention are processed in the usual manner according to processes recommended for this.
  • a silver chloride bromide emulsion with 15 mol% chloride and 85 mol% bromide, average grain diameter 0.34 ⁇ m, doped with 0.17 ⁇ mol RhCl3 per mol Ag, is produced by adding 20 ⁇ mol sodium thiosulfate per mol Ag matured to an optimal sensitivity-fog ratio.
  • the emulsion contains 100 g AgNO3 per kg.
  • This emulsion is sensitized with a green sensitizer in the amount specified (Table 1) and, after adding a wetting agent, is poured onto PE paper with a silver coating of 1.4 g per m2.
  • the gradation differentiation when exposed behind yellow and purple filters in the green sensitizers according to the invention is very good and, within certain limits, is only slightly dependent on the amount of dye; whereas in the case of higher amounts - 240 ⁇ mol / mol silver in this emulsion example - and in the case of green sensitizers of constitution (A or B) not according to the invention, there is no differentiation.
  • Example 2 is carried out analogously to Example 1, with an emulsion prepared according to the Kipp method Silver chloride bromide emulsion with 27 mol% bromide and 73 mol% chloride, grain size 0.30 ⁇ m, doped with 0.35 ⁇ mol RhCl3 per mol Ag, is used.
  • the results are shown in Table 3.
  • Table 3 shows that even with this emulsion with a high chloride content, a gradation differentiation is obtained with the green sensitizers of the formula I, while the comparison dyes have no differentiation.
  • Emulsion 1 and 2 The silver chloride bromide emulsions according to Examples 1 and 2, designated Emulsion 1 and 2 in this example, are sensitized with the green sensitizers of the formula I given in Table 4. However, the respective amount of dye is not added to the entire emulsion sample, but only the proportion (in%) given in column 6 of table 4. The spectrally sensitized portion is digested at 40 ° C for 20 minutes and then added to the unsensitized rest of the emulsion sample. This is followed by watering and sensitometric testing as described in Example 1.
  • Table 4 1 2nd 3rd 4th 5 6 emulsion 7 150 1.50 0.65 530 50 2nd 11 75 1.30 0.75 545 50 2nd 12th 150 1.35 0.60 545 50 2nd 26 75 1.30 0.80 545 50 2nd 27 75 1.15 0.60 550 50 2nd 28 75 1.50 0.65 550 50 2nd 1 250 1.55 0.65 525 30th 2nd 1 150 1.45 0.65 525 50 2nd 3rd 172 1.60 0.70 527 50 1 1 261 1.50 0.70 532 33 1 1 174 1.50 0.70 532 50 1 1 116 1.40 0.70 532 75 1 24th 175 1.20 0.70 560 50 1 25th 175 1.20 0.80 520 50 1
  • the emulsion samples according to Example 3 were repeated, but in each case 50% of the emulsion was green-sensitized according to the invention and 50% of the emulsion was sensitized in the blue spectral range by adding a blue sensitizer.
  • the sprue and sensitometric test were carried out as described.
  • the blue sensitivity increased the blue sensitivity behind the purple filter and in this way reduced the sensitivity distance to the high green sensitivity that is achieved with the green sensitizers according to the invention.

Claims (5)

  1. Papier noir et blanc (papier NB) à gradation variable comprenant au moins une couche photosensible d'émulsion à l'halogénure d'argent, caractérisé en ce que l'halogénure d'argent de la ou des couches d'émulsion à l'halogénure d'argent est sensibilisé au vert au moins partiellement avec un composé de formule
    Figure imgb0019
     dans laquelle
    R₁   représente un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe alcoxy,
    R₂   représente un groupe alkyle, un groupe sulfoalkyle ou un groupe carboxyalkyle,
    R₃   représente un groupe alkyle, un groupe hydroxyalkyle, un groupe acyloxyalkyle,
    R₄   représente un groupe alkyle, un groupe sulfoalkyle ou un groupe carboxyalkyle,
    R₅   représente un atome d'halogène, un groupe cyano, un groupe aminocarbonyle, un groupe trifluorométhyle ou un groupe alcoxycarbonyle,
    R₆   représente un atome d'hydrogène ou R₅,
    X⊖   représente un anion, et
    n   représente 0 ou 1,
    au moins un des radicaux R₁, R₅ et R₆ représentant un atome d'halogène,
    n est égal à 0 lorsqu'un des radicaux R₂ ou R₄ représente un groupe sulfoalkyle ou un groupe carboxyalkyle, et n est égal à 1 lorsqu'aucun des radicaux R₂ et R₄ ne représente un groupe sulfoalkyle ou un groupe carboxyalkyle,
    en une quantité de 10  d
    Figure imgb0020
     à 80  d
    Figure imgb0021
     µmoles/mole d'halogénure d'argent où d représente le diamètre moyen des grains de l'halogénure d'argent en µm.
  2. Papier NB à gradation variable selon la revendication 1, caractérisé en ce que seulement 20 à 80% en poids de l'émulsion sont sensibilisés au vert à l'aide d'un composé de formule (I).
  3. Papier NB à gradation variable selon la revendication 1, caractérisé en ce que la couche d'émulsion à l'halogénure d'argent contient un mélange constitué par 40 à 85% en poids d'émulsion sensibilisée au vert selon la revendication 1 et par 15 à 60% en poids d'émulsion sensibilisée au bleu.
  4. Papier NB à gradation variable selon la revendication 1, caractérisé en ce que la granulométrie moyenne des grains d'halogénure d'argent s'élève de 0,2 à 0,6 µm.
  5. Papier NB à gradation variable selon la revendication 1, caractérisé en ce que l'halogénure d'argent de la couche d'émulsion à l'halogénure d'argent est composé de 20 à 80 moles % de AgBr, de 80 à 20 moles % de AgCl et de 0 à 5 moles % de AgI.
EP88119073A 1987-11-24 1988-11-17 Papier noir et blanc à gradation variable Expired - Lifetime EP0317885B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3739783 1987-11-24
DE19873739783 DE3739783A1 (de) 1987-11-24 1987-11-24 Gradationsvariables sw-papier

Publications (3)

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EP0317885A2 EP0317885A2 (fr) 1989-05-31
EP0317885A3 EP0317885A3 (en) 1990-12-27
EP0317885B1 true EP0317885B1 (fr) 1994-03-16

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EP88119073A Expired - Lifetime EP0317885B1 (fr) 1987-11-24 1988-11-17 Papier noir et blanc à gradation variable

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US (1) US4987063A (fr)
EP (1) EP0317885B1 (fr)
JP (1) JPH01156735A (fr)
DE (2) DE3739783A1 (fr)
ES (1) ES2050138T3 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5219723A (en) * 1991-10-10 1993-06-15 Eastman Kodak Company Green sensitizing dyes for variable contrast photographic elements
EP0536769B1 (fr) * 1991-10-10 1995-05-24 Eastman Kodak Company Procédé de contrôle de la forme de la courbe caractéristique d'éléments photographiques à contraste variable
JPH07325361A (ja) * 1994-06-02 1995-12-12 Mitsubishi Paper Mills Ltd ハロゲン化銀写真感光材料
DE69514065T2 (de) * 1994-10-03 2000-07-06 Agfa Gevaert Nv Elektro(stato)graphisches Verfahren, das reaktive Toner verwendet
GB2303934B (en) * 1995-07-31 1998-10-28 Agfa Gevaert Ag Black and white paper with variable gradation
GB2316754B (en) * 1996-08-30 2000-09-27 Ilford Ltd Variable contrast photographic material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2384598A (en) * 1941-03-14 1945-09-11 Eastman Kodak Co Photographic material
DE3028167A1 (de) * 1980-07-25 1982-04-01 Agfa-Gevaert Ag, 5090 Leverkusen Photographisches aufzeichnungsmaterial mit variablem kontrast
JPS6180237A (ja) * 1984-09-28 1986-04-23 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光乳剤
US4791053A (en) * 1985-12-03 1988-12-13 Fuji Photo Film Co., Ltd. Silver halide photographic material
DE3605713A1 (de) * 1986-02-22 1987-08-27 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial

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ES2050138T3 (es) 1994-05-16
JPH01156735A (ja) 1989-06-20
US4987063A (en) 1991-01-22
DE3739783A1 (de) 1989-06-08
EP0317885A3 (en) 1990-12-27
EP0317885A2 (fr) 1989-05-31
DE3888460D1 (de) 1994-04-21

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