EP0100984B1 - Photographic silver halide emulsions - Google Patents

Photographic silver halide emulsions Download PDF

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Publication number
EP0100984B1
EP0100984B1 EP83107542A EP83107542A EP0100984B1 EP 0100984 B1 EP0100984 B1 EP 0100984B1 EP 83107542 A EP83107542 A EP 83107542A EP 83107542 A EP83107542 A EP 83107542A EP 0100984 B1 EP0100984 B1 EP 0100984B1
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EP
European Patent Office
Prior art keywords
silver halide
emulsion
layer
silver
ripened
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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.)
Expired
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EP83107542A
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German (de)
French (fr)
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EP0100984A3 (en
EP0100984A2 (en
Inventor
Manfred Dr. Becker
Sieghart Dipl.-Ing. Klötzer
Erik Prof. Dr. Moisar
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • 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
    • G03C2001/03535—Core-shell grains

Definitions

  • the invention relates to a photographic silver halide emulsion with silver halide grains which have a layered grain structure, the silver halide grains being chemically sensitized on their surface and a process for their preparation.
  • the invention further relates to a photographic recording material with a layer support and at least one layer which contains a silver halide emulsion according to the invention.
  • the surface of the convert emulsion obtained is then sensitized with a sulfur sensitizer. It is also known from US Pat. No. 2,983,608 to chemically sensitize conversion emulsions prepared according to US Pat. No. 2,592,250 and to use them in combination with color couplers in recording materials. Corresponding materials are also specified in DE-C-2 112 729 and US-A-3 622 318.
  • a disadvantage of the known emulsions with grains of high internal sensitivity, which are chemically sensitized on the surface in the usual way, is that their sensitometric properties and in particular their behavior towards pressure, especially when processed in the developer, are not yet satisfactory. It was found that converting emulsions, in particular, which are sensitized on the surface, are sensitive to pressure during processing and easily show signs of pressure if pressure is applied immediately after development, e.g. is caused by a transport device.
  • the object of the invention was to provide chemically sensitized silver halide emulsions and recording materials with such emulsions with improved properties.
  • the invention was based on the object of specifying such emulsions with improved pressure behavior and with improved sensitivity.
  • Silver halide grains with a layered grain structure are understood to mean silver halide grains which have a core and at least one layer enveloping the core, the properties of which is different from the core.
  • Corresponding emulsions are also referred to as core / shell emulsions in English parlance.
  • core / shell emulsions in English parlance.
  • the core and / or at least one layer of the grain is at a pAg value of max. 7, in particular if the pAg value is less than 5.0.
  • Suitable reducing agents are, for example, hydrazine, optionally as a hydrate, hydrazine derivatives, ascorbic acid, hydroquinone or formamidine sulfinic acid (thiourea dioxide).
  • Inorganic reducing agents such as stannous chloride or the above-mentioned thiourea dioxide are preferably used.
  • the amount of reducing agent added can vary within wide limits, it depends on the type of reducing agent and the silver halide and the desired effect.
  • the amount of reducing agent used in accordance with the present invention should generally not exceed 0.75x10 2 milliequivalents per gram of silver ion already precipitated.
  • the emulsions according to the invention are preferably monodisperse; generally at least 80% of the emulsion grains have a diameter which is within a deviation of ⁇ 20% from the mean grain diameter. It is of course possible to use mixtures of inventive monodisperse emulsions of different grain sizes in recording materials.
  • the silver halide grains are regular in the sense that they have no crystal defects due to twin formation.
  • the silver halide grains of the emulsion according to the invention have at least one layer rich in silver chloride, which consists of at least 25 mol% of silver chloride.
  • the arrangement of the layer rich in silver chloride in the silver halide grain is not critical in itself. This layer can either be present as a core, as a layer within the silver halide grain or as an outer shell.
  • the layer rich in silver chloride is preferably located inside the grain, preferably at least 0.05 ⁇ m below the surface.
  • the transition from the layer rich in silver chloride to layers of different silver halide composition can be formed as a sharp phase boundary or can take place continuously.
  • the silver halide grains preferably contain silver bromide or mixtures of silver bromide and silver iodide.
  • the silver halide grains can have any of the known forms, for example cubic, octahedral or the tetradecahedral mixed form.
  • the absolute value of the average grain size can fluctuate within wide limits.
  • both fine-grain silver halide emulsions with an average diameter of less than 0.5 ⁇ m, preferably less than 0.3 ⁇ m, and coarser-grain emulsions with an average grain diameter of in particular 0.5 to 2 1 ⁇ m can be used.
  • the silver halide is precipitated such that at least one layer in the silver halide grains contains at least 25 mol% of silver chloride and is adjacent to at least one layer poorer in silver chloride and that the total silver chloride content is less than 30 mol%. At least one layer of a silver halide grain is produced under reducing conditions.
  • the silver halide grains of the precipitated emulsion are chemically ripened on the surface to such an extent that the ratio R of density D r to density D u described above is at least 3.
  • the silver halide emulsions according to the invention can be prepared by methods known per se for the production of silver halide emulsions with a layered grain structure. It is preferable to use double enema procedures, in which the maintenance of the required pAg and pH values can best be controlled. In general, a pAg value of 10 to 7 and a pH value of 4.5 to 7 are maintained in the known precipitation methods in emulsion production. According to the invention, however, at least one layer of the silver halide grain is used under reducing conditions, in particular with a pAg value of max. 7 manufactured.
  • Complexes of multivalent cations for example those of Rh, Pd, Ir, Pt, may also be present in the preparation of the emulsion.
  • the individual precipitation stages in emulsion production can be carried out directly one after the other, but also at intervals.
  • the silver halide grains can be treated with oxidizing agents, for example with Hg 2 + or Fe 3 + compounds, in a manner known per se to suppress fog.
  • the silver halide grains according to the invention have a core which consists essentially of silver bromide, at least one layer rich in silver chloride with at least 30 mol% of silver chloride and a layer essentially containing silver bromide which is further away from the core than the layer rich in silver chloride and which contains less silver chloride than the layer rich in silver chloride.
  • sensitizers are suitable for chemical sensitization of the silver halide grains on their surface.
  • Sulfur-containing compounds for example allyl isothiocyanate, allyl thiourea and thiosulfates, are particularly preferred.
  • Reducing agents e.g. the tin compounds described in Belgian patents 493,464 or 568,687, also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, e.g. according to Belgian patent 547 323.
  • Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss.Phot. 46, 65-72 (1951). It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, e.g.
  • condensation products with polyethylene oxide with a molecular weight between 1000 and 20,000, also with condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
  • the condensation products have a molecular weight of at least 700, preferably more than 1000.
  • these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982.
  • the present invention further relates to a recording material with a layer support, at least one light-sensitive silver halide emulsion layer and optionally further layers, characterized in that an emulsion according to the invention is contained in at least one layer.
  • This recording material is preferably a color photographic recording material.
  • Silver halide emulsions with silver halide grains which have a layered grain structure and a relatively chloride-rich layer, are already known from German laid-open publications 2 308 239 and 2 332 802 and US Patents 3 935 014 and 3 957 488.
  • the surface of these emulsions is not or only slightly sensitized chemically and, if they are applied to a carrier in the usual way, exposed and developed in a surface developer, only to a very low density.
  • Silver halide emulsions are also known from German Offenlegungsschrift 2 203 462 and US Pat. No. 3,892,574. When they are precipitated or physically ripened, a pAg value between 7 and 0 is maintained at least temporarily.
  • the surface of the emulsions obtained can be chemically sensitized and have a narrow grain size distribution.
  • the emulsions can have a layered grain structure, in which case the core of the silver halide grain can be chemically sensitized and the shell can be veiled by customary methods in order to obtain emulsions of the so-called direct positive type.
  • emulsions with a layered grain structure are used which according to the invention have a layer which is relatively rich in silver chloride and are chemically sensitized on their surface.
  • German Offenlegungsschrift 3 144 867 discloses emulsions with silver halide grains and special diketo compounds.
  • the silver halide grains can have different layers and can still be precipitated at a pAg of 5 to 11.
  • silver halide emulsions with reduction-sensitized grains are known which contain phenol derivatives to improve the shelf life.
  • the silver halide grains can be made by various methods, including by a core-shell process.
  • the present invention can be applied to both black and white and color photographic images.
  • Colored photographic images can e.g. according to the known principle of chromogenic development in the presence of color couplers, which react with the oxidation product of coloring p-phenylenediamine developers to form dyes.
  • the color couplers can be added to the color developer, for example, according to the principle of the so-called development process.
  • the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers.
  • the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or a-naphthol type.
  • the green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or imidazolone type usually being used.
  • the blue-sensitive layer can for example, a non-diffusing color coupler for generating the yellow partial color image, usually a color coupler with an open-chain ketomethylene group.
  • Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publications "Farbkuppler” by W. Pelz in “Mitanderen aus der Anlagenslaboratorien der Agfa, Leverkusen / Ober", volume 111, page 111 (1961), K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971) and TH James, “The Theory of the Photographic Process", 4th Ed., Pp. 353-362.
  • the color couplers can be, for example, 6-, 4- and 2-equivalent couplers, including the so-called white couplers, which do not produce any dye when reacted with color developer oxidation products, and DIR couplers.
  • color coupler mixtures can be used to set a desired color or reactivity.
  • water-soluble couplers can be used in combination with hydrophobic water-insoluble couplers.
  • the emulsions according to the invention are particularly suitable for color photographic recording materials with at least one silver halide emulsion layer unit for recording light from each of the three spectral ranges red, green and blue.
  • Each of these layer units can comprise a single silver halide emulsion layer or also several silver halide emulsion layers.
  • Color photographic recording materials with double layers for the different spectral ranges are known, for example, from US Pat. Nos. 3,663,228,3,849,138 and 4,184,876.
  • the emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • Such sensitizers are in the work of F.M. Hamer "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition. Volume 18, pages 431 ff.
  • Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. in the article by Birr, Z.Wiss.Phot. 47, 1952), pp. 2-58.
  • Other suitable stabilizers include heterocyclic mercapto compounds, e.g. Phenyl mercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.
  • the usual substrates can be used for the materials according to the invention, e.g. Carriers made of cellulose esters such as cellulose acetate or cellulose acetobutyrate, furthermore polyesters, in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane. Also suitable are paper supports, which may contain waterproof polyolefin layers, e.g. made of polyethylene or polypropylene, can also contain supports made of glass or metal.
  • hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
  • Proteins especially gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
  • the layers can also contain other synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
  • synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
  • the layers of the photographic material can be hardened in the usual manner, for example with formaldehyde, with hardeners of the epoxy type, the heterocyclic ethyleneimine and the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German laid-open specification 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type.
  • black and white developer compounds are suitable for black and white development, e.g. the hydroxybenzenes and 3-pyrazolidones.
  • Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, for example 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N- ⁇ - (methanesulfonamido) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate, 4-amino-3- ⁇ - (methanesulfonamido) ethyl-N, N-diethylaniline hydrochloride; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine. Further useful color developers are described, for
  • the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
  • the usual compounds can be used as bleaching agents, for example Fe 3 + salts and Fe3 + complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc.
  • Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid acid, N-hydroxymethyl acetate, N-hydroxymethyl acid and of corresponding phosphonic acids.
  • a silver bromide emulsion with an average particle size of 0.25 ⁇ m was produced within 15 minutes by simultaneous pAg-controlled entry of a KBr and an AgNO 3 solution into a 2.1% gelatin solution brought to a temperature of 63 ° C.
  • the crystals of this starting emulsion were then enlarged to twice the diameter by further addition of KBr and AgNO 3 solution at pAg 6.0.
  • an AgCI shell was struck on the crystals present by pAg-controlled double entry of KCI and AgN0 3 solution.
  • the precipitation was then continued again by double entry of the KBr and AgNO 3 solution, an AgBr shell being applied to the previously precipitated AgCI layer.
  • the average particle diameter of the crystals obtained was 0.65 ⁇ m. 15% of the crystals were outside a range of 0.65 ⁇ (0.1. 0.65 1 im), ie the emulsion obtained was homodisperse.
  • the total AgCI content was 10 mol%.
  • the emulsion was freed of the soluble salts by washing in the customary manner and finally adjusted to a pAg of 7.8. Thereafter, the emulsion was ripened by adding sodium thiosulfate pentahydrate in an amount of 80 ⁇ mol / mol silver and 42.5 mg of a triazaindolizine at 45 ° C for 120 minutes.
  • the comparative emulsion K is a converting emulsion which was produced in a modification of the method known from US Pat. No. 2,592,250. According to US Pat. No. 2,592,250, conversion emulsions with a relatively broad grain size distribution are generally obtained; a distribution width is typical in which about 70% of the grains have a diameter which deviates by more than 10% from the mean diameter.
  • a converting emulsion with a narrow particle size distribution was prepared by first precipitating a monodisperse silver chloride emulsion (particle diameter 0.63 ⁇ m) by controlled double entry.
  • Emulsion K was converted by adding an equivalent amount of potassium bromide at 60 ° C for 26 minutes.
  • the conversion emulsion obtained (Emulsion K) still contained 10 mol% of silver chloride.
  • the mean grain diameter was 0.67 ⁇ m, 17% of the grains had a diameter that deviated from the mean diameter by more than 10%.
  • the dispersity of the emulsion A according to the invention and the comparison emulsion K is comparable.
  • Emulsion K was chemically ripened in the same way as Emulsion A.
  • An emulsion B according to the invention was prepared as in Example 1 under emulsion A with the modification that the silver bromide precipitation on the AgCl-containing zone was carried out not at pAg 6 but at pAg 4.5. The precipitation of the remaining layers and all other measures were carried out as indicated in Example 1.
  • the sensitometric evaluation gave the values listed in Table 2, from which the gain in sensitivity by precipitation at a lower pAg value can be clearly recognized.
  • Emulsion A prepared according to the invention has a much lower susceptibility to wet pressure than comparison emulsion K.
  • Emulsions A and K according to Example 1 were used for the layer structure given below.
  • emulsion A 1 kg of emulsion A is mixed with a coupler emulsate.
  • the coupler emulsifier is prepared from 50 mmol of a conventional yellow coupler, 13.5 ml of tricresyl phosphate and 50 ml of ethyl acetate and dispersion in 300 ml of a 12% gelatin solution in the presence of 2 g of sodium dodecylbenzenesulfonate.
  • the mixture of coupler emulsate and silver halide emulsion obtained is poured onto a customary layer support and subjected to the following processing:
  • the corresponding baths have the following compositions:

Description

Die Erfindung betrifft eine fotografische Silberhalogenidemulsion mit Silberhalogenidkörnern, die einen geschichteten Kornaufbau aufweisen, wobei die Silberhalogenidkörner an ihrer Oberfläche chemisch sensibilisiert sind und ein Verfahren zu ihrer Herstellung. Weiterhin betrifft die Erfindung ein fotografisches Aufzeichnungsmaterial mit einem Schichtträger und wenigstens einer Schicht, die eine erfindungsgemäße Silberhalogenidemulsion enthält.The invention relates to a photographic silver halide emulsion with silver halide grains which have a layered grain structure, the silver halide grains being chemically sensitized on their surface and a process for their preparation. The invention further relates to a photographic recording material with a layer support and at least one layer which contains a silver halide emulsion according to the invention.

Es ist allgemein bekannt, Silberhalogenidemulsionen, deren Körner eine hohe Innenempfindlichkeit aufweisen, herzustellen. Verwiesen wird beispielsweise auf die gemäß der US-A- 2 592 250 nach der Konvertmethode hergestellten Emulsionen sowie auf Emulsionen, deren Silberhalogenidkörner einen geschichteten Kornaufbau besitzen, wie sie beispielsweise aus der DE-B- 1 169 290 und der GB-A- 1 027 146 bekannt sind.It is generally known to prepare silver halide emulsions, the grains of which have a high internal sensitivity. Reference is made, for example, to the emulsions prepared by the conversion method in accordance with US Pat. No. 2,592,250 and to emulsions whose silver halide grains have a layered grain structure, as described, for example, in DE-B-1 169 290 and GB-A-1 027 146 are known.

Es ist weiterhin bekannt, Emulsionen mit Körnern hoher Innenempfindlichkeit an der Oberfläche in üblicher Weise chemisch zu sensibilisieren. Verwiesen wird beispielsweise auf die US-A- 3 206 313, Spalte 1, Zeile 23 ff. Hiernach wird durch übliche chemische Sensibilisierung die Oberflächenempfindlichkeit von Konvertemulsionen erhöht. Die US-A- 3 317 322 bezieht sich auf Silberhalogenidemulsionen mit einem geschichteten Kornaufbau und hoher Innenempfindlichkeit die an ihrer Oberfläche chemisch sensibilisiert sind. Aus der US-A- 2 756 148 ist es bekannt, eine Konvertemulsion z.B. dadurch herzustellen, daß zunächst eine Silberchloridbromidemulsion gefällt wird und diese anschließend durch Bromid konvertiert wird. Anschließend wird die erhaltene Konvertemulsion an ihrer Oberfläche mit einem Schwefel-Sensibilisierungsmittel sensibilisiert. Auch aus der US-A- 2 983 608 ist es bekannt, nach der US-A- 2 592 250 hergestellte Konvertemulsionen chemisch zu sensibilisieren und zusammen mit Farbkupplern in Aufzeichnungsmaterialien zu verwenden. Entsprechende Materialien werden schließlich auch in der DE-C- 2 112 729 und der US-A- 3 622 318 angegeben.It is also known to chemically sensitize emulsions with grains of high internal sensitivity on the surface in the usual way. Reference is made, for example, to US Pat. No. 3,206,313, column 1, line 23 et seq. Thereafter, the surface sensitivity of conversion emulsions is increased by conventional chemical sensitization. US-A-3 317 322 relates to silver halide emulsions with a layered grain structure and high internal sensitivity which are chemically sensitized on their surface. From US-A-2 756 148 it is known to use a conversion emulsion e.g. by first precipitating a silver chloride bromide emulsion and then converting it to bromide. The surface of the convert emulsion obtained is then sensitized with a sulfur sensitizer. It is also known from US Pat. No. 2,983,608 to chemically sensitize conversion emulsions prepared according to US Pat. No. 2,592,250 and to use them in combination with color couplers in recording materials. Corresponding materials are also specified in DE-C-2 112 729 and US-A-3 622 318.

Ein Nachteil der bekannten Emulsionen mit Körnern hoher Innenempfindlichkeit, die an der Oberfläche in üblicher Weise chemisch sensibilisiert sind, ist, daß ihre sensitometrischen Eigenschaften und insbesondere ihr Verhalten gegenüber Druck, speziell bei der Verarbeitung im Entwickler, noch nicht befriedigend sind. Es stellte sich heraus, daß insbesondere an der Oberfläche sensibilisierte Konvertemulsionen bei der Verarbeitung empfindlich gegenüber Druck sind und leicht Druckspuren aufweisen, wenn unmittelbar nach Beginn der Entwicklung eine Druckeinwirkung, z.B. durch eine Transporteinrichtung, hervorgerufen wird.A disadvantage of the known emulsions with grains of high internal sensitivity, which are chemically sensitized on the surface in the usual way, is that their sensitometric properties and in particular their behavior towards pressure, especially when processed in the developer, are not yet satisfactory. It was found that converting emulsions, in particular, which are sensitized on the surface, are sensitive to pressure during processing and easily show signs of pressure if pressure is applied immediately after development, e.g. is caused by a transport device.

Die Erscheinung, daß durch Druckeinwirkung generell Schleier hervorgerufen werden kann, ist allgemein bekannt. Verwiesen wird z.B. auf T.H. James "The Theory of the Photographic Process", 4. Auflage, Macmillan Publishing Co., Inc., New York, Seite 24. Gemäß der britischen Patentanmeldung 2 023 863 sollen die Einwirkungen durch Druck im trockenen Zustand durch den Zusatz bestimmter Verbindungen vermieden werden. Gegenüber Emulsionen, die keine Innenempfindlichkeit aufweisen soll gemäß der DE-C- 2112 729 und der US-A- 3 622 318 eine Verbesserung durch Verwendung oberflächlich sensibilisierter Konvertemulsionen erreicht werden.The phenomenon that fog can generally be caused by the action of pressure is generally known. Is referenced e.g. on T.H. James "The Theory of the Photographic Process", 4th edition, Macmillan Publishing Co., Inc., New York, page 24. According to British patent application 2 023 863, the effects of pressure in the dry state are to be avoided by the addition of certain compounds . Compared to emulsions which have no internal sensitivity, according to DE-C-2112 729 and US-A-3 622 318 an improvement can be achieved by using superficially sensitized conversion emulsions.

Der Schutz fotografischer Aufzeichnungsmaterialien vor den Folgen der Einwirkung von Druck, insbesondere vor dem Naßdruckschleier, ist aber immer noch unbefriedigend.However, the protection of photographic recording materials from the effects of pressure, in particular from the wet pressure haze, is still unsatisfactory.

Der Erfindung lag die Aufgabe zugrunde, an der Oberfläche chemisch sensibilisierte Silberhalogenidemulsionen und Aufzeichnungsmaterialien mit derartigen Emulsionen mit verbesserten Eigenschaften bereitzustellen. Insbesondere lag der Erfindung die Aufgabe zugrunde, derartige Emulsionen mit verbessertem Verhalten gegenüber Druck und mit verbesserter Empfindlichkeit anzugeben.The object of the invention was to provide chemically sensitized silver halide emulsions and recording materials with such emulsions with improved properties. In particular, the invention was based on the object of specifying such emulsions with improved pressure behavior and with improved sensitivity.

Es wurde nun eine neue fotografische Silberhalogenidemulsion mit Silberhalogenidkörnern gefunden, die einen geschichteten Kornaufbau aufweisen und die an ihrer Oberfläche chemisch sensibilisiert sind. Erfindungsgemäß enthalten die Silberhalogenidkörner wenigstens eine Schicht, die wenigstens 25 Mol-% Silberchlorid enthält, wobei der Silberchloridgehalt des gesamten Silberhalogenidkorns weniger als 30 Mol-% beträgt. Die erfindungsgemäße Emulsion ist oberflächlich so stark chemisch gereift, daß das Verhältnis R der Dichte Dr erhältlich nach der Oberflächenreifung zu der Dichte Du erhältlich mit der noch nicht oberflächlich gereiften aber ansonsten identischen Emulsion wenigstens 3 beträgt,
wobei zur Bestimmung von R die gereifte und die ungereifte Emulsion jeweils in identischer Weise auf einen Schichtträger aufgetragen, belichtet und im nachstehenden Entwickler der Zusammensetzung

  • Ascorbinsäure 10 g
  • p-Methylaminophenol 2,4 g
  • Na2C03 (sicc) 10 9
  • KBr 2,0 g
  • Wasser auf 1000 ml
  • 17 Minuten bei 20° C entwickelt werden und wobei Dr der Wert von 90 % der Maximaldichte ist und Du erhalten wird durch diejenige Belichtung der noch nicht gereiften Emulsion, die bei der gereiften Emulsion zur Dichte Dr führt.
A new photographic silver halide emulsion with silver halide grains has now been found which has a layered grain structure and which is chemically sensitized on its surface. According to the invention, the silver halide grains contain at least one layer which contains at least 25 mol% of silver chloride, the silver chloride content of the entire silver halide grain being less than 30 mol%. The surface of the emulsion according to the invention is so chemically ripened that the ratio R of the density D r obtainable after surface ripening to the density D u obtainable with the not yet surface-ripened but otherwise identical emulsion is at least 3,
where, in order to determine R, the ripened and the unripened emulsion are each applied in an identical manner to a layer support, exposed and in the developer of the composition below
  • Ascorbic acid 10 g
  • p-methylaminophenol 2.4 g
  • Na 2 CO 3 (sicc) 10 9
  • KBr 2.0 g
  • Water to 1000 ml
  • Developed 17 minutes at 20 ° C and where D r is the value of 90% of the maximum density and D u is obtained by the exposure of the not yet ripened emulsion, which leads to the density D r in the ripened emulsion.

Unter Silberhalogenidkörnern mit einem geschichteten Kornaufbau werden Silberhalogenidkörner verstanden, die einen Kern und wenigstens eine den Kern umhüllende Schicht aufweisen, die in ihren Eigenschaften vom Kern unterschieden ist. Im englischen Sprachgebrauch werden entsprechende Emulsionen auch als Core/Shell-Emulsionen bezeichnet, Selbstverständlich kann ein derartiges Silberhalogenidkorn um den Kern herum nicht nur eine Hüllenschicht sondern mehrere aufweisen. In einer bevorzugten Ausführungsform wird wenigstens zeitweise bei der Herstellung der Emulsion unter reduzierenden Bedingungen gearbeitet. In einer besonders bevorzugten Ausführungsform der Erfindung wird der Kern und/oder wenigstens eine Schicht des Korns bei einem pAg-Wert von max. 7, insbesondere bei einem pAg-Wert kleiner als 5,0, hergestellt. Es ist aber auch möglich, die reduzierenden Verhältnisse durch Anwendung üblicher Reduktionsmittel zu erreichen. Geeignete reduzierende Mittel sind z.B. Hydrazin, gegebenenfalls als Hydrat, Hydrazinderivate, Ascorbinsäure, Hydrochinon oder Formamidinsulfinsäure (Thioharnstoffdioxid). Vorzugsweise werden anorganische Reduktionsmittel, wie z.B. Zinn(II)-chlorid oder das genannte Thioharnstoffdioxid verwendet. Die zugesetzte Menge an Reduktionsmittel kann innerhalb weiter Grenzen schwanken, sie hängt ab von der Art des Reduktionsmittels und des Silberhalogenids sowie dem gewünschten Effekt. Die angewendete Menge an reduzierendem Mittel gemäß der vorliegenden Erfindung sollte im allgemeinen 0,75x102 Milliäquivalent pro g bereits gefälltes Silberion nicht übersteigen. In den meisten Fällen haben sich Mengen von 0,1 bis 10 mg/kg Silbernitrat als ausreichend erwiesen. Im Falle des Thioharnstoffdioxids genügen z.B. Mengen von 0,5 bis 7,0 mg. Die erfindungsgemäßen Emulsionen sind vorzugsweise monodispers; im allgemeinen weisen mindestens 80% der Emulsionskörner einen Durchmesser auf, der innerhalb einer Abweichung von ± 20 % vom mittleren Korndurchmesser liegt. Selbstverständlich ist es möglich, in Aufzeichnungsmaterialien Abmischungen erfindungsgemäßer monodisperser Emulsionen unterschiedlicher Korngröße zu verwenden. In einer bevorzugten Ausführungsform sind die Silberhalogenidkörner regulär in dem Sinne, daß sie keine Kristallfehler durch Zwillingsbildung aufweisen.Silver halide grains with a layered grain structure are understood to mean silver halide grains which have a core and at least one layer enveloping the core, the properties of which is different from the core. Corresponding emulsions are also referred to as core / shell emulsions in English parlance. Of course, such a silver halide grain around the core can have not only one shell layer but several. In a preferred embodiment, at least occasionally, the emulsion is produced under reducing conditions. In a particularly preferred embodiment of the invention, the core and / or at least one layer of the grain is at a pAg value of max. 7, in particular if the pAg value is less than 5.0. However, it is also possible to achieve the reducing ratios by using customary reducing agents. Suitable reducing agents are, for example, hydrazine, optionally as a hydrate, hydrazine derivatives, ascorbic acid, hydroquinone or formamidine sulfinic acid (thiourea dioxide). Inorganic reducing agents such as stannous chloride or the above-mentioned thiourea dioxide are preferably used. The amount of reducing agent added can vary within wide limits, it depends on the type of reducing agent and the silver halide and the desired effect. The amount of reducing agent used in accordance with the present invention should generally not exceed 0.75x10 2 milliequivalents per gram of silver ion already precipitated. In most cases, amounts of 0.1 to 10 mg / kg silver nitrate have proven to be sufficient. In the case of thiourea dioxide, amounts of 0.5 to 7.0 mg, for example, are sufficient. The emulsions according to the invention are preferably monodisperse; generally at least 80% of the emulsion grains have a diameter which is within a deviation of ± 20% from the mean grain diameter. It is of course possible to use mixtures of inventive monodisperse emulsions of different grain sizes in recording materials. In a preferred embodiment, the silver halide grains are regular in the sense that they have no crystal defects due to twin formation.

Die Silberhalogenidkörner der erfindungsgemäßen Emulsion weisen wenigstens eine silberchloridreiche Schicht auf, die wenigstens zu 25 Mol-% aus Silberchlorid besteht. Die Anordnung der silberchloridreichen Schicht im Silberhalogenidkorn ist an sich nicht kritisch. Diese Schicht kann entweder als Kern, als eine Schicht innerhalb des Silberhalogenidkorns oder als eine äußere Hülle vorhanden sein. Vorzugsweise befindet sich die silberchloridreiche Schicht im Korninneren, und zwar vorzugsweise mindestens 0,05um unterhalb der Oberfläche. Der Übergang von der silberchloridreichen Schicht zu Schichten anderer Silberhalogenidzusammensetzung kann als scharfe Phasengrenze ausgebildet sein oder kontinuierlich erfolgen.The silver halide grains of the emulsion according to the invention have at least one layer rich in silver chloride, which consists of at least 25 mol% of silver chloride. The arrangement of the layer rich in silver chloride in the silver halide grain is not critical in itself. This layer can either be present as a core, as a layer within the silver halide grain or as an outer shell. The layer rich in silver chloride is preferably located inside the grain, preferably at least 0.05 μm below the surface. The transition from the layer rich in silver chloride to layers of different silver halide composition can be formed as a sharp phase boundary or can take place continuously.

Neben dem Silberchlorid enthalten die Silberhalogenidkörner vorzugsweise Silberbromid oder Gemische aus Silberbromid und Silberjodid.In addition to the silver chloride, the silver halide grains preferably contain silver bromide or mixtures of silver bromide and silver iodide.

Die Silberhalogenidkörner können irgendeine der bekannten Formen aufweisen, z.B. kubisch, oktaedrisch oder auch die tetradekaedrische Mischform. Der Absolutwert der mittleren Korngröße kann innerhalb weiter Grenzen schwanken. Je nach dem gewünschten Verwendungszweck können sowohl feinkörnige Silberhalogenidemulsionen mit einem mittleren Durchmesser von unter 0,5µm, vorzugsweise unter 0,3µm, als auch grobkörnigere Emulsionen mit einem mittleren Korndurchmesser von insbesondere 0,5 bis 21im verwendet werden.The silver halide grains can have any of the known forms, for example cubic, octahedral or the tetradecahedral mixed form. The absolute value of the average grain size can fluctuate within wide limits. Depending on the intended use, both fine-grain silver halide emulsions with an average diameter of less than 0.5 μm, preferably less than 0.3 μm, and coarser-grain emulsions with an average grain diameter of in particular 0.5 to 2 1 μm can be used.

Beim Verfahren zur Herstellung einer erfindungsgemäßen fotografischen Silberhalogenidemulsion
wird die Fällung des Silberhalogenids derart vorgenommen, daß in den Silberhalogenidkörnern wenigstens eine Schicht wenigstens 25 Mol-% Silberchlorid enthält und mindestens einer Silberchlorid ärmeren Schicht benachbart ist und daß der Gesamtgehalt an Silberchlorid weniger als 30 Mol-% beträgt. Dabei erfolgt die Herstellung wenigstens einer Schicht eines Silberhalogenidkorns unter reduzierenden Bedingungen.In the process for producing a photographic silver halide emulsion according to the present invention
the silver halide is precipitated such that at least one layer in the silver halide grains contains at least 25 mol% of silver chloride and is adjacent to at least one layer poorer in silver chloride and that the total silver chloride content is less than 30 mol%. At least one layer of a silver halide grain is produced under reducing conditions.

Dann werden die Silberhalogenidkörner der gefällten Emulsion oberflächlich so stark chemisch gereift, daß das oben beschriebene Verhältnis R der Dichte Dr zu der Dichte Du wenigstens 3 beträgt.Then the silver halide grains of the precipitated emulsion are chemically ripened on the surface to such an extent that the ratio R of density D r to density D u described above is at least 3.

Die erfindungsgemäßen Silberhalogenidemulsionen können nach an sich bekannten Methoden für die Herstellung von Silberhalogenidemulsionen mit geschichtetem Kornaufbau hergestellt werden. Dabei werden vorzugsweise Doppeleinlaufverfahren angewendet, bei denen die Aufrechterhaltung der erforderlichen pAg- und pH-Werte am besten kontrolliert werden kann. Im allgemeinen wird bei den bekannten Fällungsmethoden bei der Emulsionsherstellung ein pAg-Wert von 10 bis 7 und ein pH-Wert von 4,5 bis 7 eingehalten. Erfindungsgemäß wird aber wenigstens eine Schicht des Silberhalogenidkorns unter reduzierenden Bedingungen, insbesondere bei einem pAg-Wert von max. 7 hergestellt. Bei der Emulsionsherstellung können fernerhin Komplexe mehrwertiger Kationen, z.B. solche des Rh, Pd, lr, Pt anwesend sein. Die einzelnen Fällungsstufen bei der Emulsionsherstellung können direkt hintereinander, aber auch in Abständen getrennt vorgenommen werden. Nach Abschluß der Fällung können die Silberhalogenidkörner zur Unterdrückung von Schleier in an sich bekannter Weise mit Oxidationsmitteln, z.B. mit Hg2+- oder Fe3+-Verbindungen behandelt werden.The silver halide emulsions according to the invention can be prepared by methods known per se for the production of silver halide emulsions with a layered grain structure. It is preferable to use double enema procedures, in which the maintenance of the required pAg and pH values can best be controlled. In general, a pAg value of 10 to 7 and a pH value of 4.5 to 7 are maintained in the known precipitation methods in emulsion production. According to the invention, however, at least one layer of the silver halide grain is used under reducing conditions, in particular with a pAg value of max. 7 manufactured. Complexes of multivalent cations, for example those of Rh, Pd, Ir, Pt, may also be present in the preparation of the emulsion. The individual precipitation stages in emulsion production can be carried out directly one after the other, but also at intervals. After the precipitation has ended, the silver halide grains can be treated with oxidizing agents, for example with Hg 2 + or Fe 3 + compounds, in a manner known per se to suppress fog.

In einer bevorzugten Ausführungsform weisen die erfindungsgemäßen Silberhalogenidkörner einen Kern auf, der im wesentlichen aus Silberbromid besteht, wenigstens eine silberchloridreiche Schicht mit wenigstens 30 Mol-% Silberchlorid sowie eine im wesentlichen Silberbromid enthaltende Schicht, die vom Kern weiter entfernt liegt als die silberchloridreiche Schicht und die weniger Silberchlorid als die silberchloridreiche Schicht enthält.In a preferred embodiment, the silver halide grains according to the invention have a core which consists essentially of silver bromide, at least one layer rich in silver chloride with at least 30 mol% of silver chloride and a layer essentially containing silver bromide which is further away from the core than the layer rich in silver chloride and which contains less silver chloride than the layer rich in silver chloride.

Zur chemischen Sensibilisierung der Silberhalogenidkörner an ihrer Oberfläche sind die üblichen Sensibilisierungsmittel geeignet. Besonders bevorzugt sind schwefelhaltige Verbindungen, beispielsweise Allylisothiocyanat, Allylthioharnstoff und Thiosulfate.The usual sensitizers are suitable for chemical sensitization of the silver halide grains on their surface. Sulfur-containing compounds, for example allyl isothiocyanate, allyl thiourea and thiosulfates, are particularly preferred.

Als chemische Sensibilisatoren können ferner auch Reduktionsmittel, z.B. die in den belgischen Patentschriften 493 464 oder 568 687 beschriebenen Zinnverbindungen, ferner Polyamine wie Diethylentriamin oder Aminomethylsulfinsäure-Derivate, z.B. gemäß der belgischen Patentschrift 547 323, verwendet werden. Geeignet als chemische Sensibilisatoren sind auch Edelmetalle bzw. Edelmetallverbindungen wie Gold, Platin, Palladium, Iridium, Ruthenium oder Rhodium. Diese Methode der chemischen Sensibilisierung ist in dem Artikel von R. Koslowsky, Z.Wiss.Phot. 46, 65-72 (1951), beschrieben. Es ist ferner möglich, die Emulsionen mit Polyalkylenoxid-Derivaten zu sensibilisieren, z.B. mit Polyethylenoxid eines Molekulargewichts zwischen 1000 und 20 000, ferner mit Kondensationsprodukten von Alkylenoxiden und aliphatischen Alkoholen, Glykolen, cyclischen dehydratisierungsprodukten von Hexitolen, mit alkylsubstituierten Phenolen, aliphatischen Carbonsäuren, aliphatischen Aminen, aliphatischen Diaminen und Amiden. Die Kondensationsprodukte haben ein Molekulargewicht von mindestens 700, vorzugsweise von mehr als 1000. Zur Erzielung besonderer Effekte kann man diese Sensibilisatoren selbstverständlich kombiniert verwenden, wie in der belgischen Patentschrift 537 278 und in der britischen Patentschrift 727 982 beschrieben.Reducing agents, e.g. the tin compounds described in Belgian patents 493,464 or 568,687, also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, e.g. according to Belgian patent 547 323. Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss.Phot. 46, 65-72 (1951). It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, e.g. with polyethylene oxide with a molecular weight between 1000 and 20,000, also with condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides. The condensation products have a molecular weight of at least 700, preferably more than 1000. To achieve special effects, these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982.

Die vorliegende Erfindung betrifft weiterhin ein Aufzeichnungsmaterial mit einem Schichtträger, wenigstens einer lichtempfindlichen Silberhalogenidemulsionsschicht und gegebenenfalls weiteren Schichten, dadurch gekennzeichnet, daß in wenigstens einer Schicht eine erfindungsgemäße Emulsion enthalten ist. Vorzugsweise handelt es sich bei diesem Aufzeichnungsmaterial um ein farbfotografisches Aufzeichnungsmaterial.The present invention further relates to a recording material with a layer support, at least one light-sensitive silver halide emulsion layer and optionally further layers, characterized in that an emulsion according to the invention is contained in at least one layer. This recording material is preferably a color photographic recording material.

Aus den deutschen Offenlegungsschriften 2 308 239 und 2 332 802 sowie den US-Patenten 3 935 014 und 3 957 488 sind zwar bereits Silberhalogenidemulsionen mit Silberhalogenidkörnern bekannt, die einen geschichteten Kornaufbau und eine relativ chloridreiche Schicht aufweisen; diese Emulsionen werden aber an ihrer Oberfläche nicht oder nur gering chemisch sensibilisiert und führen, wenn sie in üblicher Weise auf einen Träger aufgetragen, belichtet und in einem Oberflächenentwickler entwickelt werden nur zu einer sehr geringen Dichte.Silver halide emulsions with silver halide grains, which have a layered grain structure and a relatively chloride-rich layer, are already known from German laid-open publications 2 308 239 and 2 332 802 and US Patents 3 935 014 and 3 957 488. However, the surface of these emulsions is not or only slightly sensitized chemically and, if they are applied to a carrier in the usual way, exposed and developed in a surface developer, only to a very low density.

Aus der deutschen Offenlegungsschrift 2 203 462 und dem US-Patent 3 892 574 sind weiterhin Silberhalogenidemulsionen bekannt, bei deren Fällung oder bei deren physikalischer Reifung wenigstens zeitweise ein pAg-Wert zwischen 7 und 0 eingehalten wird. Die erhaltenen Emulsionen können an ihrer Oberfläche chemisch sensibilisiert sein und eine enge Korngrößenverteilung aufweisen. Weiterhin können die Emulsionen einen geschichteten Kornaufbau besitzen, wobei dann der Kern des Silberhalogenidkorns chemisch sensibilisiert sein kann und die Schale durch übliche Methoden verschleiert sein kann, um Emulsionen des sog. Direktpositiv-Typs zu erhalten. Es erfolgt aber kein Hinweis darauf, Emulsionen mit einem geschichteten Kornaufbau zu verwenden, die erfindungsgemäß eine relativ silberchloridreiche Schicht aufweisen und an ihrer Oberfläche chemisch sensibilisiert sind.Silver halide emulsions are also known from German Offenlegungsschrift 2 203 462 and US Pat. No. 3,892,574. When they are precipitated or physically ripened, a pAg value between 7 and 0 is maintained at least temporarily. The surface of the emulsions obtained can be chemically sensitized and have a narrow grain size distribution. Furthermore, the emulsions can have a layered grain structure, in which case the core of the silver halide grain can be chemically sensitized and the shell can be veiled by customary methods in order to obtain emulsions of the so-called direct positive type. However, there is no indication that emulsions with a layered grain structure are used which according to the invention have a layer which is relatively rich in silver chloride and are chemically sensitized on their surface.

Aus der deutschen Offenlegungsschrift 3 144 867 sind Emulsionen mit Silberhalogenidkörnern und speziellen Diketoverbindungen bekannt. Die Silberhalogenidkörner können verschiedene Schichten aufweisen und sie können weiterhin bei einem pAg-Wert von 5 bis 11 gefällt werden. Aus der deutschen Offenlegungsschrift 3 144 313 sind Silberhalogenidemulsionen mit Reduktionssensibilisierten Körnern bekannt, die zur Verbesserung der Lagerbeständigkeit Phenolderivate enthalten. Die Silberhalogenidkörner können nach verschiedenen Verfahren, u.a. nach einem Kern-Hüllen-Verfahren, hergestellt werden.German Offenlegungsschrift 3 144 867 discloses emulsions with silver halide grains and special diketo compounds. The silver halide grains can have different layers and can still be precipitated at a pAg of 5 to 11. From German Offenlegungsschrift 3 144 313, silver halide emulsions with reduction-sensitized grains are known which contain phenol derivatives to improve the shelf life. The silver halide grains can be made by various methods, including by a core-shell process.

Die vorliegende Erfindung kann sowohl für die Herstellung schwarz-weißer als auch farbiger fotografischer Bilder angewendet werden. Farbige fotografische Bilder können z.B. nach dem bekannten Prinzip der chromogenen Entwicklung in Anwesenheit von Farbkupplern, die mit dem Oxidationsprodukt von farbgebenden p-Phenylendiamin-Entwicklern unter Bildung von Farbstoffen reagieren, hergestellt werden.The present invention can be applied to both black and white and color photographic images. Colored photographic images can e.g. according to the known principle of chromogenic development in the presence of color couplers, which react with the oxidation product of coloring p-phenylenediamine developers to form dyes.

Die Farbkuppler können beispielsweise dem Farbentwickler nach dem Prinzip des sogenannten Einentwicklungsverfahrens zugesetzt werden. In einer bevorzugten Ausführungsform enthält das fotografische Material selbst die üblichen Farbkuppler, die in der Regel den Silberhalogenidschichten einverleibt sind. So kann die rotempfindliche Schicht beispielsweise einen nicht- diffundierenden Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes enthalten, in der Regel einen Kuppler von Phenol- oder a-Naphtholtyp. Die grünempfindliche Schicht kann beispielsweise mindestens einen nichtdiffundierenden Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes enthalten, wobei üblicherweise Farbkuppler vom Typ des 5-Pyrazolons oder des Imidazolons Verwendung finden. Die blauempfindliche Schicht kann beispielsweise einen nicht-diffundierenden Farbkuppler zur Erzeugung des gelben Teilfarbenbildes, in der Regel einen Farbkuppler mit einer offenkettigen Ketomethylengruppierung enthalten. Farbkuppler dieser Art sind in großer Zahl bekannt und in einer Vielzahl von Patentschriften beschrieben. Beispielhaft sei hier auf die Veröffentlichungen "Farbkuppler" von W. Pelz in "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen/München", Band 111, Seite 111 (1961), K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 bis 387, Academic Press (1971) und T.H. James, "The Theory of the Photographic Process", 4. Ed., S. 353-362 verwiesen. Bei den Farbkupplern kann es sich z.B. um 6-, 4- und um 2-Äquivalentkuppler handeln, darunter die sogenannten Weißkuppler, die bei Reaktion mit Farbentwickleroxidationsprodukten keinen Farbstoff ergeben, sowie DIR-Kuppler.The color couplers can be added to the color developer, for example, according to the principle of the so-called development process. In a preferred embodiment, the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers. For example, the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or a-naphthol type. The green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or imidazolone type usually being used. The blue-sensitive layer can for example, a non-diffusing color coupler for generating the yellow partial color image, usually a color coupler with an open-chain ketomethylene group. Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publications "Farbkuppler" by W. Pelz in "Mitteilungen aus der Forschungslaboratorien der Agfa, Leverkusen / München", volume 111, page 111 (1961), K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971) and TH James, "The Theory of the Photographic Process", 4th Ed., Pp. 353-362. The color couplers can be, for example, 6-, 4- and 2-equivalent couplers, including the so-called white couplers, which do not produce any dye when reacted with color developer oxidation products, and DIR couplers.

Bei Bedarf können Farbkupplermischungen verwendet werden, um einen gewünschten Farbton oder eine gewünschte Reaktivität einzustellen. Beispielsweise können wasserlösliche Kuppler in Kombination mit hydrophoben wasserunlöslichen Kupplern verwendet werden.If necessary, color coupler mixtures can be used to set a desired color or reactivity. For example, water-soluble couplers can be used in combination with hydrophobic water-insoluble couplers.

Die erfindungsgemäßen Emulsionen sind insbesondere für farbfotografische Aufzeichnungsmaterialien mit mindestens je einer Silberhalogenidemulsionsschichten-Einheit für die Aufzeichnung von Licht jedes der drei Spektralbereiche Rot, Grün und Blau geeignet. Jede dieser Schichteinheiten kann eine einzige Silberhalogenidemulsionsschicht oder auch mehrere Silberhalogenidemulsionsschichtenumfassen. Farbfotografische Aufzeichnungsmaterialien mit Doppelschichten für die verschiedenen Spektralbereiche sind beispielsweise aus den US-Patentschriften 3 663 228.3 849 138 und 4 184 876 bekannt.The emulsions according to the invention are particularly suitable for color photographic recording materials with at least one silver halide emulsion layer unit for recording light from each of the three spectral ranges red, green and blue. Each of these layer units can comprise a single silver halide emulsion layer or also several silver halide emulsion layers. Color photographic recording materials with double layers for the different spectral ranges are known, for example, from US Pat. Nos. 3,663,228,3,849,138 and 4,184,876.

Die Emulsionen können in an sich bekannter Weise optisch sensibilisiert werden, z.B. mit den üblichen Polymethinfarbstoffen, wie Neutrocyaninen, basischen oder sauren Carbocyaninen, Rhodacyaninen, Hemicyaninen, Styrylfarbstoffen, Oxonolen und ähnlichen. Derartige Sensibilisatoren sind in dem Werk von F.M. Hamer "The Cyanine Dyes and related Compounds", (1964), beschrieben. Verwiesen sei diesbezüglich insbesondere auf Ullmanns Enzyklopädie der technischen Chemie, 4. Auflage. Band 18, Seiten 431 ff.The emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like. Such sensitizers are in the work of F.M. Hamer "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition. Volume 18, pages 431 ff.

Als Stabilisatoren sind besonders geeignet Azaindene, vorzugsweise Tetra- oder Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind z.B. in dem Artikel von Birr, Z.Wiss.Phot. 47,1952), S. 2-58, beschrieben. Weitere geeignete'Stabilisatoren sind u.a. heterocyclische Mercaptoverbindungen, z.B. Phenylmercaptotetrazol, quaternäre Benzthiazolderivate und Benzotriazol.Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. in the article by Birr, Z.Wiss.Phot. 47, 1952), pp. 2-58. Other suitable stabilizers include heterocyclic mercapto compounds, e.g. Phenyl mercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.

Für die erfindungsgemäßen Materialien können die üblichen Schichtträger verwendet werden, z.B. Träger aus Celluloseestern wie Celluloseacetat oder Celluloseacetobutyrat, ferner Polyester, insbesondere Polyethylenterephthalat oder Polycarbonate, insbesondere auf Basis von Bisphenylolpropan. Geeignet sind ferner Papierträger, die gegebenenfalls wasserundurchlässige Polyolefinschichten, z.B. aus Polyethylen oder Polypropylen, enthalten können, ferner Träger aus Glas oder Metall.The usual substrates can be used for the materials according to the invention, e.g. Carriers made of cellulose esters such as cellulose acetate or cellulose acetobutyrate, furthermore polyesters, in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane. Also suitable are paper supports, which may contain waterproof polyolefin layers, e.g. made of polyethylene or polypropylene, can also contain supports made of glass or metal.

Als Schutzkolloid bzw. Bindemittel für die Schichten des Aufzeichnungsmaterials sind die üblichen hydrophilen filmbildenden Mittel geeignet, z.B. Proteine, insbesondere Gelatine, Alginsäure oder deren Derivate wie Ester, Amide oder Salze, Cellulose-Derivate wie Carboxymethycellulose und Cellulosesulfate, Stärke oder deren Derivate oder hydrophile synthetische Bindemittel wie Polyvinylalkohol, teilweise verseiftes Polyvinylacetat, Polyvinylpyrrolidon und andere. Die Schichten können im Gemisch mit den hydrophilen Bindemitteln auch andere synthetische Bindemittel in gelöster oder dispergierter Form enthalten wie Homo- oder Copolymerisate von Acryloder Methacrylsäure oder deren Derivaten wie Estern, Amiden oder Nitrilen, ferner Vinylpolymerisate wie Vinylester oder Vinylether.The usual hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others. In a mixture with the hydrophilic binders, the layers can also contain other synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.

Die Schichten des fotografischen Materials können in der üblichen Weise gehärtet sein, beispielsweise mit Formaldehyd, mit Härtern des Epoxidtyps, des heterocyclischen Ethylenimins und des Acryloyltyps. Weiterhin ist es auch möglich, die Schichten gemäß dem Verfahren der deutschen Offenlegungsschrift 2 218 009 zu härten, um farbfotografische Materialien zu erzielen, die für eine Hochtemperaturverarbeitung geeignet sind. Es ist ferner möglich, die fotografischen Schichten bzw. die farbfotografischen Mehrschichtenmaterialien mit Härtern der Diazin-, Triazin- oder 1,2-Dihydrochinolin-Reihe zu härten oder mit Härtern vom Vinylsulfon-Typ.The layers of the photographic material can be hardened in the usual manner, for example with formaldehyde, with hardeners of the epoxy type, the heterocyclic ethyleneimine and the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German laid-open specification 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type.

Bezüglich weiterer geeigneter Zusätze zu den erfindungsgemäßen farbfotografischen Aufzeichnungsmaterialien oder zu einer seiner Schichten sei verwiesen auf den Artikel in der Zeitschrift "Product Licensing Index", Band 92, Dezember 1971, Seiten 107 bis 110.With regard to further suitable additives to the color photographic recording materials according to the invention or to one of its layers, reference is made to the article in the magazine "Product Licensing Index", volume 92, December 1971, pages 107 to 110.

Für eine Schwarzweißentwicklung sind die üblichen bekannten Schwarzweißentwicklerverbindungen geeignet, wie z.B. die Hydroxybenzole und 3-Pyrazolidone.The usual known black and white developer compounds are suitable for black and white development, e.g. the hydroxybenzenes and 3-pyrazolidones.

Geeignete Farbentwicklersubstanzen für das erfindungsgemäße Material sind insbesondere solche vom p-Phenylendiamintyp, z.B. 4-Amino-N,N-diethyl-anilinhydrochlorid; 4-Amino-3-methyl-N-ethyl-N-ß-(methansulfonamido)ethylanilinsulfathydrat; 4-Amino-3-methyl-N-ethyl-N-ß- hydroxyethylanilinsulfat, 4-Amino-3-ß-(methansulfonamido) -ethyl-N,N-diethylanilinhydrochlorid; 4-Amino-N-ethyl-N-(2-methoxyethyl)-m-toluidin-di-p-toluolsulfonsäure und N-Ethyl-N-ß-hydroxyethyl-p-phenylendiamin. Weitere brauchbare Farbentwickler sind beispielsweise beschrieben in J.Amer.Chem.Soc. 73, 3100 (1951) und in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, Seiten 545 ff.Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, for example 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N-β- (methanesulfonamido) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-β- (methanesulfonamido) ethyl-N, N-diethylaniline hydrochloride; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine. Further useful color developers are described, for example, in J.Amer.Chem.Soc. 73, 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pages 545 ff.

Nach der Farbentwicklung wird das Material üblicherweise gebleicht und fixiert. Bleichung und Fixierung können getrennt voneinander oder auch zusammen durchgeführt werden. Als Bleichmittel können die üblichen Verbindungen verwenget werden, z.B. Fe3+-Salze und Fe3+-Komplexsalze wie Ferricyanide, Dichromate, wasserlösliche Kobaltkomplexe usw. Besonders bevorzugt sind Eisen-III-Komplexe von Aminopolycarbonsäuren, insbesondere z.B. Ethylendiamintetraessigsäure, Nitrilotriessigsäure, Iminodiessigsäure, N-Hydroxyethylethylendiamintriessigsäure und von entsprechenden Phosphonsäuren.After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. The usual compounds can be used as bleaching agents, for example Fe 3 + salts and Fe3 + complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc. Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid acid, N-hydroxymethyl acetate, N-hydroxymethyl acid and of corresponding phosphonic acids.

Beispiel 1example 1 Erfindungsgemäße Emulsion AEmulsion A according to the invention

Durch gleichzeitigen pAg-gesteuerten Einlauf einer KBr-und einer AgN03-Lösung zu einer auf eine Temperatur von 63° C gebrachten 2,1 %igen Gelatinelösung wurde innerhalb von 15 Minuten eine Silberbromidemulsion mit einer mittleren Teilchengröße von 0,25.µm hergestellt. Anschließend wurden die Kristalle dieser Ausgangsemulsion durch weitere Zugabe von KBr- und AgN03-Lösung bei pAg 6,0 auf den doppelten Durchmesser vergrößert. Anschließend wurde durch pAg-gesteuerten Doppeleinlauf von KCI- und AgN03-Lösung eine AgCI-Hülle auf die vorliegenden Kristalle aufgefällt. Die Fällung wurde anschließend erneut durch Doppeleinlauf von KBr- und AgN03-Lösung fortgesetzt, wobei eine AgBr-Hülle auf die zuvor aufgefällte AgCI-Schicht aufgebracht wurde. Der mittlere Teilchendurchmesser der erhaltenen Kristalle betrug 0,65µm. 15 % der Kristalle lagen außerhalb eines Bereiches von 0,65 ± (0,1. 0,651im), d.h. die erhaltene Emulsion war homodispers. Der Gesamtgehalt an AgCI betrug 10 Mol-%.A silver bromide emulsion with an average particle size of 0.25 μm was produced within 15 minutes by simultaneous pAg-controlled entry of a KBr and an AgNO 3 solution into a 2.1% gelatin solution brought to a temperature of 63 ° C. The crystals of this starting emulsion were then enlarged to twice the diameter by further addition of KBr and AgNO 3 solution at pAg 6.0. Subsequently, an AgCI shell was struck on the crystals present by pAg-controlled double entry of KCI and AgN0 3 solution. The precipitation was then continued again by double entry of the KBr and AgNO 3 solution, an AgBr shell being applied to the previously precipitated AgCI layer. The average particle diameter of the crystals obtained was 0.65 μm. 15% of the crystals were outside a range of 0.65 ± (0.1. 0.65 1 im), ie the emulsion obtained was homodisperse. The total AgCI content was 10 mol%.

Die Emulsion wurde in üblicher Weise durch Waschen von den löslichen Salzen befreit und abschließend auf einen pAg-Wert von 7,8 eingestellt. Danach wurde die Emulsion durch Zugabe von Natriumthiosulfatpentahydrat in einer Menge von 80µmol/Mol Silber und von 42,5 mg eines Triazaindolizins 120 Minuten lang bei 45° C gereift.The emulsion was freed of the soluble salts by washing in the customary manner and finally adjusted to a pAg of 7.8. Thereafter, the emulsion was ripened by adding sodium thiosulfate pentahydrate in an amount of 80 µmol / mol silver and 42.5 mg of a triazaindolizine at 45 ° C for 120 minutes.

Vergleichsemulsion KComparative emulsion K

Die Vergleichsemulsion K ist eine Konvertemulsion, die in Abwandlung der aus der US-A- 2 592 250 bekannten Methode hergestellt wurde. Nach der US-A- 2 592 250 werden in Regel Konvertemulsionen mit relativ breiter Korngrössenverteilung erhalten; typisch ist eine Verteilungsbreite, bei der etwa 70 % der Körner einen Durchmesser haben, der um mehr als 10 % vom mittleren Durchmesser abweicht. Um zum Vergleich eine Konvertemulsion ähnlich enger Korngrößenverteilung wie bei der erfindungsgemäßen Emulsion A zu erhalten, wurde eine Konvertemulsion enger Korngrößenverteilung dadurch hergestellt, daß zunächst durch gesteuerten Doppeleinlauf eine monodisperse Silberchloridemulsion (Korndurchmesser 0,63µm) gefällt wurde. Diese Emulsion wurde durch Zugabe einer äquivalenten Menge an Kaliumbromid 26 Minuten lang bei 60° C konvertiert. Die erhaltene Konvertemulsion (Emulsion K) enthielt noch 10 Mol-% Silberchlorid. Der mittlere Korndurchmesser betrug 0,67µm, 17 % der Körner wiesen einen Durchmesser auf, der um mehr als 10 % vom mittleren Durchmesser abwich. Die Dispersität der erfindungsgemäßen Emulsion A und der Vergleichsemulsion K ist vergleichbar. Die Emulsion K wurde in der gleichen Weise wie die Emulsion A chemisch gereift.The comparative emulsion K is a converting emulsion which was produced in a modification of the method known from US Pat. No. 2,592,250. According to US Pat. No. 2,592,250, conversion emulsions with a relatively broad grain size distribution are generally obtained; a distribution width is typical in which about 70% of the grains have a diameter which deviates by more than 10% from the mean diameter. In order to obtain a conversion emulsion with a similarly narrow particle size distribution as in the case of emulsion A according to the invention, a converting emulsion with a narrow particle size distribution was prepared by first precipitating a monodisperse silver chloride emulsion (particle diameter 0.63 μm) by controlled double entry. This emulsion was converted by adding an equivalent amount of potassium bromide at 60 ° C for 26 minutes. The conversion emulsion obtained (Emulsion K) still contained 10 mol% of silver chloride. The mean grain diameter was 0.67 µm, 17% of the grains had a diameter that deviated from the mean diameter by more than 10%. The dispersity of the emulsion A according to the invention and the comparison emulsion K is comparable. Emulsion K was chemically ripened in the same way as Emulsion A.

Beide Emulsionen wurden jeweils in gleicher Weise auf einen Cellulosetriacetat-Schichtträger vergossen, hinter einem Graukeil belichtet und mit einem üblichen Schwarzweißentwickler entwickelt. Die sensitometrischen Werte sind in der folgenden Tabelle 1 angegeben:

Figure imgb0001
Both emulsions were cast in the same way on a cellulose triacetate support, exposed behind a gray wedge and developed with a conventional black and white developer. The sensitometric values are given in Table 1 below:
Figure imgb0001

Eine Verdoppelung des unter "Empfindlichkeit" angegebenen Wertes entspricht einer Verdoppelung der Empfindlichkeit selbst.Doubling the value specified under "Sensitivity" corresponds to doubling the sensitivity itself.

Aus Tabelle 1 ist zu ersehen, daß die erfindungsgemäße Emulsion A bei geringerem Schleier eine deutlich höhere Empfindlichkeit aufweist.It can be seen from Table 1 that the emulsion A according to the invention has a significantly higher sensitivity with a lower fog.

Beispiel 2Example 2 Erfindungsgemäße Emulsion BEmulsion B according to the invention

Eine erfindungsgemäße Emulsion B wurde wie in Beispiel 1 unter Emulsion A mit der Abänderung hergestellt, daß die Silberbromidauffällung auf die AgCI-haltige Zone nicht bei pAg 6 sondern bei pAg 4,5 durchgeführt wurde. Die Auffällung der übrigen Schichten sowie sämtliche weiteren Maßnahmen wurden wie in Beispiel 1 angegeben durchgeführt. Die sensitometrische Auswertung ergab die in Tabelle 2 aufgeführten Werte, aus denen der Empfindlichkeitsgewinn durch Fällung bei niedrigerem pAg-Wert deutlich erkennbar ist.An emulsion B according to the invention was prepared as in Example 1 under emulsion A with the modification that the silver bromide precipitation on the AgCl-containing zone was carried out not at pAg 6 but at pAg 4.5. The precipitation of the remaining layers and all other measures were carried out as indicated in Example 1. The sensitometric evaluation gave the values listed in Table 2, from which the gain in sensitivity by precipitation at a lower pAg value can be clearly recognized.

Figure imgb0002
Figure imgb0002

Beispiel 3Example 3

Dieses Beispiel belegt, daß die erfindungsgemäß hergestellte Emulsion A eine sehr viel geringere Naßdruckanfälligkeit besitzt als Vergleichsemulsion K. Für den im folgenden angegebenen Schichtaufbau wurden die Emulsionen A und K gemäß Beispiel 1 verwendet.This example proves that emulsion A prepared according to the invention has a much lower susceptibility to wet pressure than comparison emulsion K. Emulsions A and K according to Example 1 were used for the layer structure given below.

Für einen erfindungsgemäßen Schichtaufbau wird 1 kg der Emulsion A mit einem Kuppleremulgat vermischt. Das Kuppleremulgat wird hergestellt aus 50 mmol eines üblichen Gelbkupplers, 13,5 ml Trikresylphosphat und 50 ml Ethylacetat und Dispergierung in 300 ml einer 12 %igen Gelatinelösung in Gegenwart von 2 g Natriumdodecylbenzolsulfonat. Die erhaltene Mischung aus Kuppleremulgat und Silberhalogenidemulsion wird auf einen üblichen Schichtträger vergossen und folgender Verarbeitung unterworfen:

Figure imgb0003
Die entsprechenden Bäder haben folgende Zusammensetzungen:For a layer structure according to the invention, 1 kg of emulsion A is mixed with a coupler emulsate. The coupler emulsifier is prepared from 50 mmol of a conventional yellow coupler, 13.5 ml of tricresyl phosphate and 50 ml of ethyl acetate and dispersion in 300 ml of a 12% gelatin solution in the presence of 2 g of sodium dodecylbenzenesulfonate. The mixture of coupler emulsate and silver halide emulsion obtained is poured onto a customary layer support and subjected to the following processing:
Figure imgb0003
 The corresponding baths have the following compositions:

FarbentwicklungslösungColor development solution

  • Benzylalkohol 15 mlBenzyl alcohol 15 ml
  • Kaliumcarbonat 30 gPotassium carbonate 30 g
  • Kaliumbromid 0,5 gPotassium bromide 0.5 g
  • Hydroxylaminsulfat 2 gHydroxylamine sulfate 2 g
  • Natriumsulfit 2 gSodium sulfite 2 g
  • Diethylentriamin 1 gDiethylenetriamine 1 g
  • N-Ethyl-N-ß-methansulfonamidoethyl-3-methyl-4-aminoanilinsulfat 4,5 gN-ethyl-N-ß-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g
  • auffüllen mit Wasser auf 1 Ifill up to 1 I with water
Bleich-/FixierlösungBleaching / fixing solution

  • Ammoniumthiosulfat (70 %) 150 mlAmmonium thiosulfate (70%) 150 ml
  • Natriumsulfit 5 gSodium sulfite 5 g
  • Na [Fe (EDTA)] 40 gNa [Fe (EDTA)] 40 g
  • EDTA 4 gEDTA 4 g
  • auffüllen mit Wasser auf 1 Ifill up to 1 I with water

In entsprechender Weise wurde ein Vergleichsmaterial hergestellt mit der Abänderung, daß anstelle der erfindungsgemäßen Emulsion A die Vergleichsemulsion K verwendet wurde.In a corresponding manner, a comparison material was produced with the modification that the comparison emulsion K was used instead of the emulsion A according to the invention.

Zur Prüfung der Druckempfindlichkeit wurde auf beide Materialien unmittelbar nach Beginn der Entwicklung eine Druckspur aufgebracht. Nach Abschluß der Verarbeitung wurden die getrockneten Materialien dann mit einem Mikrodensitometer ausgemessen. Aus den in Tabelle 3 angegebenen Ergebnissen ist der sehr viel geringere Naßdruckschleier der erfindungsgemäßen Materialien ersichtlich. Die in Tabelle 3 angegebenen Stufen X, Y und Z stehen für unterschiedliche Belichtungsintensitäten.To test the sensitivity to pressure, a pressure trace was applied to both materials immediately after development began. After processing was complete, the dried materials were then measured with a microdensitometer. The much lower wet pressure haze of the materials according to the invention can be seen from the results given in Table 3. The levels X, Y and Z given in Table 3 stand for different exposure intensities.

Figure imgb0004
Figure imgb0004

Claims (10)

1. Photographic silver halide emulsion containing silver halide grains which have a layered grain structure and whose surface is chemically sensitised, characterised in that, in the silver halide grains, at least one layer contains at least 25 mol % of silver chloride and is directly adjacent to at least one layer which has a lower silver chloride content, in that the total content of silver chloride is less than 30 mol % and in that the emulsion according to the invention is chemically surface-ripened to such a degree that the ratio R of the density Dr obtainable after surface ripening to the density Du obtainable with the as yet non-surface-ripened, but otherwise identical emulsion is at least 3, R being determined by applying the ripened and the unripened emulsion to a layer support in an identical manner, exposing them and developing them in the following developer of the composition
ascorbic acid 10 g
p-methylaminophenyl 2.4 g
Na2C03 (sicc) 10 g
KBr 2.5 g
water to 1000 ml
for 17 minutes at 20° C, and Dr being the value of 90% of the maximum density and Du being obtained by an exposure of the unripened emulsion which leads to the density Dr in the ripened emulsion.
2. Photographic silver halide emulsion according to Claim 1, characterised in that it is monodisperse and the silver halide grains are regular.
3. Photographic silver halide emulsion according to Claim 1, characterised in that the silver halide grains have a core which consists essentially of silver bromide, at least one layer containing at least 30 mol % of silver chloride and at least one outer layer which consists essentially of silver bromide.
4. Photographic silver halide emulsion according to Claim 1, characterised in that the total content of silver chloride is at most 20 mol 0/0.
5. Photographic recording material comprising a layer support, at least one photosensitive silver halide emulsion layer and optionally other layers, characterised in that an emulsion according to Claim 1 is contained in at least one layer.
6. Photographic recording material according to Claim 5, characterised in that a colour coupler is contained in at least one layer of the recording material.
7. Process for the production of a photographic silver halide emulsion containing silver halide grains which have a layered structure composed of several layers by precipitation of the silver halide and subsequent chemical ripening of the grain surface, characterised in that
1) the precipitation is carried out in such a manner that, in the silver halide grains, at least one layer contains at least 25 mol % of silver chloride and is adjacent to at least one layer which has a lower silver chloride content and in that the total content of silver chloride is less than 30 mol %.
2) the silver halide grains of the precipitated emulsion are chemically surface-ripened to such a degree that the ratio R of the density Dr obtainable after surface-ripening to the density Du obtainable with the as yet non-surface-ripened, but otherwise identical, emulsion is at least 3, R being determined by applying the ripened and the unripened emulsion to a layer support in an identical manner, exposing them and developing them in the following developer of the composition
ascorbic acid 10 g
p-methylaminophenyl 2.4 g
Na2C03 (sicc) 10 g
KBr 2.0 g
water to 1000 ml
for 17 minutes at 20° C, and Dr being the value of 90% of the maximum density and Du being obtained by an exposure of the unripened emulsion which leads to the density Dr in the ripened emulsion and
3) the production of at least one layer of the silver halide grain is carried out under reducing conditions.
8. Process for the production of a photographic silver halide emulsion according to Claim 7, characterised in that at least one layer of the silver halide grains is precipitated at a pAg value of at most 7.
9. Process for the production of a photographic silver halide emulsion according to Claim 7, characterised in that at least one layer of the silver halide grains is precipitated at a pAg value of less than 5.0.
10. Process for the production of a photographic silver halide emulsion according to Claim 7, characterised in that the surface of the silver halide grains is chemically ripened with a sulphur sensitiser.
EP83107542A 1982-08-12 1983-08-01 Photographic silver halide emulsions Expired EP0100984B1 (en)

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JPS6055821B2 (en) * 1981-02-18 1985-12-06 富士写真フイルム株式会社 Manufacturing method of internal latent image type silver halide photographic emulsion
JPS57138631A (en) * 1981-02-19 1982-08-27 Fuji Photo Film Co Ltd Internal latent image type silver halide emulsion
JPS599653A (en) * 1982-07-08 1984-01-19 Konishiroku Photo Ind Co Ltd Silver halide photosensitive material
JPS5948755A (en) * 1982-09-13 1984-03-21 Konishiroku Photo Ind Co Ltd Silver halide photographic emulsion

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0232865A2 (en) 1986-02-07 1987-08-19 Fuji Photo Film Co., Ltd. Light-sensitive material containing silver halide, reducing agent and polymerizable compound

Also Published As

Publication number Publication date
DE3367032D1 (en) 1986-11-20
DE3229999A1 (en) 1984-02-16
JPS59140444A (en) 1984-08-11
US4495277A (en) 1985-01-22
EP0100984A3 (en) 1984-09-26
JPH0616157B2 (en) 1994-03-02
EP0100984A2 (en) 1984-02-22

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