EP0029127B1 - Method for hardening a photographic material, and photosensitive material - Google Patents

Method for hardening a photographic material, and photosensitive material Download PDF

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Publication number
EP0029127B1
EP0029127B1 EP80106380A EP80106380A EP0029127B1 EP 0029127 B1 EP0029127 B1 EP 0029127B1 EP 80106380 A EP80106380 A EP 80106380A EP 80106380 A EP80106380 A EP 80106380A EP 0029127 B1 EP0029127 B1 EP 0029127B1
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EP
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Prior art keywords
compound
hardening
photographic
denotes
hardened
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EP80106380A
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German (de)
French (fr)
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EP0029127A1 (en
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Peter Dr. Bergthaller
Wolfgang Dr. Himmelmann
Johannes Dr. Sobel
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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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners

Definitions

  • the invention relates to a process for hardening a photographic material or photographic layers which contain proteins and in particular gelatin as binders, and to a light-sensitive silver halide photographic material hardened by the process.
  • metal salts such as chromium, aluminum or zirconium salts, aldehydes and halogen-containing aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric acid, 1,2- and 1,4-diketones such as cyclohexanedione-1,2 and quinones and chlorides of 2-basic organic acids, the anhydrides of tetracarboxylic acids, compounds with several reactive vinyl groups such as vinyl sulfones, acrylamides, compounds with at least two easily cleavable, heterocyclic 3-membered rings such as ethylene oxide and ethylene imine, polyfunctional methanesulfonic acid esters and bis-chloroacylamido compounds.
  • metal salts such as chromium, aluminum or zirconium salts, aldehydes and halogen-containing aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric acid, 1,2- and 1,4-
  • high molecular weight curing agents such as. B. polyaceolein or its derivatives or copolymers and alginic acid derivatives known, which are used specifically as layer-limited curing agents.
  • the use of the compounds mentioned for photographic purposes is associated with a number of serious disadvantages. Some of these compounds are photographically active and are therefore unsuitable for hardening photographic materials, others influence the physical properties, such as e.g. B. the fragility of the gelatin layers so disadvantageous that they can not be used. Others cause discoloration or a change in pH during the curing reaction. In addition, it is particularly important for the hardening of photographic layers that the hardening reaches its maximum as soon as possible after drying, so that the permeability of the material to be hardened to the developer solution does not change continuously, as in the case of mucochloric acid or formaldehyde, for example .
  • crosslinking agents for gelatin also have a skin-damaging effect, such as. B. the ethyleneimine compounds, so that their application is not appropriate for physiological reasons.
  • the hardening of the compounds after some time is good, but the compounds are sparingly soluble in water, which can lead to irregularities in the hardening within the layer.
  • Particular problems arise with the increasingly rapid processing of photographic, especially color photographic, materials, which places increased demands on the mechanical properties and the swelling behavior of the materials.
  • the known hardening agents either caused new difficulties or simply proved unsuitable.
  • divinyl sulfone DE-C-872153
  • the use of divinyl sulfone prevents its toxicity.
  • DE-C-1 100 942 aromatic vinylsulfone compounds and DE-A-1 147 733 have disclosed nitrogen or oxygen as heteroatoms containing heterocyclic vinylsulfone compounds.
  • DE-C-1 808 685 and DE-A-2348194 describe bis-vinylsulfonylalkyl compounds as curing agents.
  • the known vinyl sulfone compounds have proven to be disadvantageous as curing agents in several respects. They are either not sufficiently water-soluble and require special measures to be used in gelatin photographic layers enable, or they adversely affect the drying behavior of the layers. Other of these compounds increase the viscosity of the casting compositions so as to interfere with the processing of the casting compositions into layers.
  • Known hardeners of the vinyl sulfone type also cause migration of photographic additives from one layer to the other, particularly in color photographic recording materials, which causes color changes and those of the photographic properties.
  • gelatin-curing products A disadvantage of these gelatin-curing products is that the formation of high-molecular by-products cannot be avoided when they are formed.
  • the by-products that arise in an uncontrollable manner are no longer or barely able to diffuse within a photographic layer structure. They remain in the layer in which they were initially introduced and cause overcuring there, which depends on the amount of by-products formed and is therefore not controllable.
  • the object of the invention is now to provide a photographic recording material which contains a hardening agent with improved properties.
  • the invention relates to a method for curing a photographic material with a compound containing vinylsulfonyl groups as a crosslinking agent, which is characterized in that a bisulfite addition product containing at least two free vinylsulfonyl groups in the molecule of a compound which contains up to 6 vinylsulfonyl groups as crosslinking agents is used.
  • crosslinking agents (curing agents) used according to the invention correspond to the general formula
  • the invention further relates to a photosensitive silver halide photographic material which has been hardened by this process.
  • the curing agents (crosslinkers) of the invention contain at least 2 vinylsulfonyl groups and at least one sulfonethanesulfonic acid group in the molecule. They are water-soluble and are excellent cross-linking agents for gelatin-containing layers.
  • the compounds are obtained by reacting the tris and polyvinyl sulfones with one mole of alkali bisulfite, or, in the case of polyvinyl sulfones, with 2 and more moles of alkali bisulfite.
  • the reaction is described in Liebigs Annalen 601, 81 (1956) in connection with monovinyl sulfones, but can easily be applied to the above compounds.
  • the molar ratio between the vinyl sulfone compounds and bisulfite can vary depending on the indication of the vinyl sulfonyl groups of the starting compound, the vinyl sulfone compound. It is only important that at least 2 vinyl sulfone groups are retained in their original form in the reaction product, because this is the only way that a crosslinking reaction with the remaining groups of gelatin is possible.
  • the hardening agents according to the invention can be added to the casting solution either some time before the casting or immediately before the casting by metering devices.
  • the compounds can also be added to an overlay solution which is used as a curing overcoat after the finished material has been prepared.
  • the finished layer structure can also be drawn through a solution with the compounds according to the invention and thereby receives the necessary amount of hardening agent. All known curing agents can be used for pre-curing the material.
  • the curing agents according to the invention by adding only to the intermediate layers in the overall layer structure. This system has advantages because the casting solutions for intermediate layers generally contain less gelatin and therefore no problems due to changes in viscosity can arise.
  • the curing agents according to the invention are generally used in an amount of from 0.01 to 15% by weight and preferably from 0.1 to 10% by weight, based on the dry weight of the gelatin in the coating solution.
  • the time of addition to the coating solution is not critical, but silver halide emulsions will expediently be added to the hardener after chemical ripening.
  • photographic layers are to be understood very generally as layers which are used in the context of photographic materials, for example light-sensitive silver halide emulsion layers, protective layers, filter layers, antihalo layers, backing layers or very generally photographic auxiliary layers.
  • the curing method according to the invention is excellently suitable
  • layers which are based on non-sensitized emulsions, X-ray emulsions and other spectrally sensitized emulsions there may be mentioned, for example, layers which are based on non-sensitized emulsions, X-ray emulsions and other spectrally sensitized emulsions.
  • the hardening process of the invention has proven itself for hardening the gelatin layers used for the various black and white and color photographic processes, such as negative, positive and diffusion transfer processes or printing processes.
  • the process according to the invention has proven to be particularly advantageous for the hardening of photographic layer dressings which are intended for carrying out color photographic processes, e.g. B. those that contain emulsion layers with color couplers or emulsion layers that are intended for treatment with solutions containing color couplers.
  • the effect of the compounds used in the manner according to the invention is not impaired by the usual photographic additives.
  • the hardeners are indifferent to photographically active substances, such as. B. water-soluble and emulsified water-insoluble color components, stabilizers, sensitizers. Furthermore, they have no adverse effect on the light-sensitive silver halide emulsions.
  • the emulsion layers can contain known silver halides as light-sensitive components, such as silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide or silver chlorobiodobromide.
  • the emulsions can be chemically sensitized by precious metal compounds, e.g. B. by compounds of ruthenium, rhodium, palladium, iridium, platinum, gold and the like, such as ammonium chloropalladate, potassium chloroplatinate, potassium chloropalladinate, or potassium thloroaurate. You can also use special sensitizers such. B. sulfur compounds, tin (11) salts, Contain polyamines or polyalkylene oxide compounds. Furthermore, the emulsions with the usual dyes, for. B. optically sensitized with cyanine dyes, merocyanine dyes and mixed cyanine dyes.
  • the emulsions can finally all known couplers, for. B. colorless couplers or colored couplers, stabilizers such as mercury compounds, triazole compounds, azainden compounds, benzothiazolium compounds or zinc compounds, wetting agents such as dihydroxyalkanes, the film-forming properties improving agents, for. B.
  • alkyl acrylate or alkyl methacrylate / acrylic acid or methacrylic acid mixed polymers water-dispersible, particulate high polymers, styrene / maleic acid mixed polymers or styrene / maleic anhydride-semi-alkyl ester mixed polymers, coating auxiliaries, such as polyethylene glycol, as well as other photographic assistants, conventional photographic ether contain.
  • the curing agents of the invention when used in color photographic materials, the couplers, such as. B. purple couplers of the 5-pyrazolone type, cyan couplers of the naphthol or phenol type and yellow couplers of the open-chain ketomethylene type, so-called 2-equivalent and 4-equivalent couplers, which are derived from the above-mentioned couplers, and so-called masking couplers with an arylazo group contained in the active site, no color changes occur in the photographic materials.
  • the couplers such as. B. purple couplers of the 5-pyrazolone type, cyan couplers of the naphthol or phenol type and yellow couplers of the open-chain ketomethylene type, so-called 2-equivalent and 4-equivalent couplers, which are derived from the above-mentioned couplers, and so-called masking couplers with an arylazo group contained in the active site, no color changes occur in the photographic materials.
  • the hardening agents of the invention are distinguished from the known hardeners of the vinylsulfonyl type in that they cause neither immediate hardening nor so-called over-hardening of the photographic layers treated with them, which is an advantage for the production process and for the storage of photographic materials represents.
  • test specimen is developed as a black sheet in a conventional color development process and weighed after the final bath after the excess water has been stripped off. The sample is then dried and weighed again. The difference, converted from the area of the test specimen to 1 m 2 , gives the water absorption per m 2 .
  • the swelling is measured gravimetrically after treatment of a test strip in distilled water at 22 ° C. for 10 minutes. It is characterized by the swelling factor:
  • a metal tip of a defined size is passed over the wet layer and loaded with increasing weight.
  • the wet scratch resistance is indicated by the weight at which the tip leaves a visible scratch mark on the layer.
  • a high weight corresponds to a high wet scratch resistance.
  • 1 and 2 g of the compounds according to the invention are added at pH 6.2 to 100 ml of a ready-to-pour photographic silver bromide gelatin emulsion which contains 10% by weight gelatin.
  • the mixture is stirred well and immediately poured onto a prepared cellulose triacetate base using a conventional casting machine and dried.
  • the material is stored under various climatic conditions and then the crosslinking is checked by determining the layer melting point, the wet scratch resistance and the swelling factor. Good crosslinking is evident from a high layer melting point, high wet scratch resistance and a low swelling factor.
  • Table 1 shows that boil-resistant layers (melting point 100 ° C.) are obtained with the addition of 1 to 2 g hardener per 100 g gelatin. After storage at 36 ° C and 80% rel. Humidity increases the hardening in a moderate form and no over-hardening is obtained. The casting solutions can be left for 1 hour without increasing the viscosity, a sign of the advantageous low crosslinking of the gelatin in the solution. The layers showed no disadvantageous properties compared to the uncured layer after development and fixing. Sensitivity, fog values and y values did not change. The hardeners remained inert towards the halosilver emulsion even after the layers had been stored for a long time.
  • the layered structure is then dried.
  • the layers After drying, the layers had a layer melting point of 38 ° C and, due to the high swelling and the strong tendency to form wrinkles, could not be processed in baths at 20 ° C.
  • the measured values show that the hardening agent has migrated through the entire layer structure and hardened.
  • the photographic values such as sensitivity and fog were not changed.

Description

Die Erfindung betrifft ein Verfahren zur Härtung eines photographischen Materials bzw. photographischer Schichten, die als Bindemittel Proteine und insbesondere Gelatine enthalten, sowie ein nach dem Verfahren gehärtetes lichtempfindliches photographisches Silberhalogenidmaterial.The invention relates to a process for hardening a photographic material or photographic layers which contain proteins and in particular gelatin as binders, and to a light-sensitive silver halide photographic material hardened by the process.

Als Härtungsmittel für Proteine und im besonderen für Gelatine sind bereits zahlreiche Substanzen beschrieben worden. Hierzu gehören beispielsweise Metallsalze wie Chrom-, Aluminium- oder Zirkonsalze, Aldehyde und halogenhaltige Aldehydverbindungen, insbesondere Formaldehyd, Dialdehyde und Mucochlorsäure, 1,2- und ,1,4-Diketone wie Cyclohexandion-1,2 und Chinone sowie Chloride von 2-basischen organischen Säuren, die Anhydride von Tetracarbonsäuren, Verbindungen mit mehreren reaktionsfähigen Vinylgruppen wie Vinylsulfone, Acrylamide, Verbindungen mit mindestens zwei leichtspaltbaren, heterocyclischen 3gliedrigen Ringen wie Ethylenoxid und Ethylenimin, mehrfunktionelle Methansulfonsäureester und Bis-chloracylamidoverbindungen.Numerous substances have already been described as hardening agents for proteins and in particular for gelatin. These include, for example, metal salts such as chromium, aluminum or zirconium salts, aldehydes and halogen-containing aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric acid, 1,2- and 1,4-diketones such as cyclohexanedione-1,2 and quinones and chlorides of 2-basic organic acids, the anhydrides of tetracarboxylic acids, compounds with several reactive vinyl groups such as vinyl sulfones, acrylamides, compounds with at least two easily cleavable, heterocyclic 3-membered rings such as ethylene oxide and ethylene imine, polyfunctional methanesulfonic acid esters and bis-chloroacylamido compounds.

In neuerer Zeit wurden hochmolekulare Härtungsmittel, wie z. B. Polyaceolein bzw. seine Derivate oder Mischpolymerisate sowie Alginsäurederivate bekannt, die speziell als schichtbegrenzte Härtungsmittel Verwendung finden.In recent times, high molecular weight curing agents such as. B. polyaceolein or its derivatives or copolymers and alginic acid derivatives known, which are used specifically as layer-limited curing agents.

Die Verwendung der genannten Verbindungen für photographische Zwecke ist jedoch mit einer Reihe schwerwiegender Nachteile verbunden. Einige dieser Verbindungen sind photographisch aktiv und sind deshalb zur Härtung photographischer Materialien ungeeignet, andere beeinflussen die physikalischen Eigenschaften, wie z. B. die Brüchigkeit der Gelatineschichten so nachteilig, daß sie nicht verwendet werden können. Andere wiederum verursachen Verfärbungen oder eine Änderung des pH-Wertes während der Härtungsreaktion. Darüber hinaus ist es für die Härtung photographischer Schichten besonders wichtig, daß die Härtung möglichst kurze Zeit nach dem Auftrocknen ihr Maximum erreicht, damit nicht, wie beispielsweise im Falle der Mucochlorsäure oder des Formaldehyds, sich die Durchlässigkeit des zu härtenden Materials für die Entwicklerlösung fortlaufend ändert.However, the use of the compounds mentioned for photographic purposes is associated with a number of serious disadvantages. Some of these compounds are photographically active and are therefore unsuitable for hardening photographic materials, others influence the physical properties, such as e.g. B. the fragility of the gelatin layers so disadvantageous that they can not be used. Others cause discoloration or a change in pH during the curing reaction. In addition, it is particularly important for the hardening of photographic layers that the hardening reaches its maximum as soon as possible after drying, so that the permeability of the material to be hardened to the developer solution does not change continuously, as in the case of mucochloric acid or formaldehyde, for example .

In gewissen Fällen haben Vernetzungsmittel für Gelatine auch hautschädigende Wirkung, wie z. B. die Ethyleniminverbindungen, so daß ihre Anwendung schon aus physiologischen Gründen nicht angebracht ist.In certain cases, crosslinking agents for gelatin also have a skin-damaging effect, such as. B. the ethyleneimine compounds, so that their application is not appropriate for physiological reasons.

Es ist weiter bekannt, Trichlortriazin, Hydroxydichlortriazin und Dichloraminotriazine als Härtungsmittel zu verwenden. Nachteilig ist hierbei der verhältnismäßig hohe Dampfdruck, Ausfällung von Salzsäure während der Härtung und die physiologische Wirkung dieser Verbindungen. Wasserlösliche Derivate, die Carboxyl- und Sulfonsäuregruppen enthalten und die durch Umsetzung von Cyanurchlorid mit einem Mol Diaminoalkyl- oder Diaminoarylsulfonsäure oder Carbonsäure erhalten werden, zeigen diese Nachteile nicht und sind deshalb in neuerer Zeit als Härtungsmittel vorgeschlagen worden. Ihre praktische Verwendbarkeit ist jedoch begrenzt, da sie sich infolge ihrer guten Löslichkeit beim Stehen in wäßrigen Lösungen zersetzen und dadurch ihre Wirksamkeit schnell einbüßen.It is also known to use trichlorotriazine, hydroxydichlorotriazine and dichloraminotriazine as curing agents. The disadvantage here is the relatively high vapor pressure, precipitation of hydrochloric acid during the curing and the physiological effect of these compounds. Water-soluble derivatives which contain carboxyl and sulfonic acid groups and which are obtained by reacting cyanuric chloride with a mole of diaminoalkyl or diaminoarylsulfonic acid or carboxylic acid do not show these disadvantages and have therefore recently been proposed as curing agents. However, their practical usability is limited because, due to their good solubility, they decompose when standing in aqueous solutions and therefore quickly lose their effectiveness.

Es ist bei einem Härtungsmittel für photographische, gelatinehaltige Schichten sowohl aus Herstellungs- als auch aus Verarbeitungsgründen von größter Bedeutung, daß auch das Einsetzen der Vernetzungsreaktion in gewissen Grenzen bestimmbar ist, beispielsweise durch Wahl der Trocknungstemperatur oder durch Wahl des pH-Wertes.In the case of a hardening agent for photographic, gelatin-containing layers, it is of the utmost importance, both for production and processing reasons, that the onset of the crosslinking reaction can be determined within certain limits, for example by choosing the drying temperature or by choosing the pH.

Als Härtungsmittel für photographische Gelatineschichten bekannt sind weiter Verbindungen mit zwei oder mehreren Acrylsäureamidogruppen im Molekül, N,N',N"-Trisacryloylhydrotriazin oder Methylenbisacrylamid vorgeschlagen worden.Compounds having two or more acrylic acid amido groups in the molecule, N, N ', N "-trisacryloylhydrotriazine or methylenebisacrylamide, have also been proposed as hardening agents for photographic gelatin layers.

Die Härtung der Verbindungen nach einiger Zeit ist zwar gut, jedoch sind die Verbindungen in Wasser schwer löslich, was innerhalb der Schicht zu Ungleichmäßigkeiten in der Härtung führen kann. Besondere Probleme ergeben sich bei der in zunehmendem Maße gebrauchten Schnellverarbeitung photographischer, insbesondere farbphotographischer Materialien, die gesteigerte Anforderungen an die mechanischen Eigenschaften und das Quellverhalten der Materialien stellt. Dazu kommen die Schwierigkeiten, die sich aus der Notwendigkeit, immer dünnere photographische Schichten herzustellen, ergeben. Man hat versucht, solche Probleme durch Anwendung verschiedenartiger Härtungsmittel zu lösen. Die bekannten Härtungsmittel haben dabei aber entweder neue Schwierigkeiten verursacht oder sich einfach als ungeeignet erwiesen.The hardening of the compounds after some time is good, but the compounds are sparingly soluble in water, which can lead to irregularities in the hardening within the layer. Particular problems arise with the increasingly rapid processing of photographic, especially color photographic, materials, which places increased demands on the mechanical properties and the swelling behavior of the materials. In addition, there are the difficulties that arise from the need to produce ever thinner photographic layers. Attempts have been made to solve such problems by using various hardening agents. However, the known hardening agents either caused new difficulties or simply proved unsuitable.

Dazu zählen die zahlreichen bekannten Vinylsulfongruppen enthaltenden Härtungsmittel, von denen Divinylsulfon (DE-C-872153) zu den am längsten bekannten gehört. Einer Anwendung des Divinylsulfons steht seine Toxizität entgegen.These include the numerous known curing agents containing vinyl sulfone groups, of which divinyl sulfone (DE-C-872153) is one of the longest known. The use of divinyl sulfone prevents its toxicity.

Weiter sind durch die DE-C-1 100 942 aromatische Vinylsulfonverbindungen und durch die DE-A-1 147 733 Stickstoff oder Sauerstoff als Heteroatome enthaltende heterocyclische Vinylsulfonverbindungen bekanntgeworden. Schließlich beschreibt die DE-C-1 808 685 und die DE-A-2348194 Bis-vinylsulfonylalkylverbindungen als Härtungsmittel.Furthermore, DE-C-1 100 942 aromatic vinylsulfone compounds and DE-A-1 147 733 have disclosed nitrogen or oxygen as heteroatoms containing heterocyclic vinylsulfone compounds. Finally, DE-C-1 808 685 and DE-A-2348194 describe bis-vinylsulfonylalkyl compounds as curing agents.

Die bekannten Vinylsulfonverbindungen haben sich als Härtungsmittel in mehrfacher Hinsicht als nachteilhaft erwiesen. Sie sind entweder nicht hinreichend wasserlöslich und machen besondere Maßnahmen erforderlich, um ihre Anwendung in photographischen Gelatineschichten zu ermöglichen, oder sie beeinflussen das Trocknungsverhalten der Schichten in nachteiliger Weise. Andere dieser Verbindungen erhöhen die Viskosität der Gießzusammensetzungen so, daß die Verarbeitung der Gießzusammensetzungen zu Schichten gestört wird.The known vinyl sulfone compounds have proven to be disadvantageous as curing agents in several respects. They are either not sufficiently water-soluble and require special measures to be used in gelatin photographic layers enable, or they adversely affect the drying behavior of the layers. Other of these compounds increase the viscosity of the casting compositions so as to interfere with the processing of the casting compositions into layers.

Bekannte Härter des Vinylsulfontyps bewirken auch, insbesondere in farbphotographischen Aufzeichnungsmaterialien, eine Auswanderung photographischer Zusätze von einer in die andere Schicht, was Farbänderungen und solche der photographischen Eigenschaften zur Folge hat.Known hardeners of the vinyl sulfone type also cause migration of photographic additives from one layer to the other, particularly in color photographic recording materials, which causes color changes and those of the photographic properties.

Aus der DE-A-2 635 518 ist es bekannt, Gelatine, zur Härtung mit einem Produkt reagieren zu lassen, das durch Umsetzung einer mindestens drei Vinylsulfonylgruppen enthaltenden Verbindung und einer Verbindung, die mindestens eine wasserlösliche Gruppe und mindestens eine mit der Vinylsulfongruppe reagierende Gruppe enthält, hergestellt wurde.From DE-A-2 635 518 it is known to allow gelatin, for hardening, to react with a product which is obtained by reacting a compound containing at least three vinylsulfonyl groups and a compound which has at least one water-soluble group and at least one group which reacts with the vinylsulfone group contains, was produced.

Nachteilig an diesen Gelatine härtenden Produkten ist, daß bei deren Bildung die Entstehung hochmolekularer Nebenprodukte nicht zu vermeiden ist. Die in nichtkontrollierbarer Weise entstehenden Nebenprodukte sind nicht mehr oder kaum noch fähig innerhalb eines photographischen Schichtverbandes zu diffundieren. Sie verbleiben in der Schicht, in der sie zunächst eingebracht worden sind, und bewirken dort eine Überhärtung, die von der Menge der gebildeten Nebenprodukte abhängig und damit nicht steuerbar ist.A disadvantage of these gelatin-curing products is that the formation of high-molecular by-products cannot be avoided when they are formed. The by-products that arise in an uncontrollable manner are no longer or barely able to diffuse within a photographic layer structure. They remain in the layer in which they were initially introduced and cause overcuring there, which depends on the amount of by-products formed and is therefore not controllable.

Aufgabe der Erfindung ist es nun, ein photographisches Aufzeichnungsmaterial bereit zu stellen, das ein Härtungsmittel mit verbesserten Eigenschaften enthält.The object of the invention is now to provide a photographic recording material which contains a hardening agent with improved properties.

Gegenstand der Erfindung ist ein Verfahren zur Härtung eines photographischen Materials mit einer Vinylsulfonylgruppen enthaltenden Verbindung als Vernetzer, das dadurch gekennzeichnet ist, daß ein mindestens zwei freie Vinyl-Sulfonylgruppen im Molekül enthaltendes Bisulfit-Additionsprodukt einer Verbindung, die bis zu 6 Vinylsulfonylgruppen enthält, als Vernetzer verwendet wird.The invention relates to a method for curing a photographic material with a compound containing vinylsulfonyl groups as a crosslinking agent, which is characterized in that a bisulfite addition product containing at least two free vinylsulfonyl groups in the molecule of a compound which contains up to 6 vinylsulfonyl groups as crosslinking agents is used.

Die erfindungsgemäß verwendeten Vernetzer (Härtungsmittel) entsprechen der allgemeinen Formel

Figure imgb0001
The crosslinking agents (curing agents) used according to the invention correspond to the general formula
Figure imgb0001

In dieser Formel bedeutet:

  • Z einen x-wertigen, gegebenenfalls substituierten, aliphatischen Kohlenwasserstoffrest, einen x-wertigen, gegebenenfalls substituierten Cycloalkanrest, wie z. B. einen Cyclohexanrest, einen x-wertigen, gegebenenfalls substituierten Hexahydrotriazinrest, oder einen x-wertigen, gegebenenfalls substituierten aromatischen Rest, wie z. B. einen vn Benzol oder Naphthalin abgeleiteten Rest,
  • x eine ganze Zahl von 3 bis 6,
  • a x-b,
  • b 1 oder 2 und
  • Me ein Alkali- oder Ammoniumion.
In this formula:
  • Z is an x-valent, optionally substituted, aliphatic hydrocarbon radical, an x-valent, optionally substituted cycloalkane radical, such as. B. a cyclohexane radical, an x-valent, optionally substituted hexahydrotriazine residue, or an x-valent, optionally substituted aromatic radical, such as. B. a residue derived from benzene or naphthalene,
  • x is an integer from 3 to 6,
  • a xb,
  • b 1 or 2 and
  • Me an alkali or ammonium ion.

Gegenstand der Erfindung ist weiter ein nach diesem Verfahren gehärtestes lichtempfindliches photographisches Silberhalogenidmaterial.The invention further relates to a photosensitive silver halide photographic material which has been hardened by this process.

Die Härtungsmittel (Vernetzer) der Erfindung enthalten mindestens 2 Vinylsulfonylgruppen und mindestens eine Sulfonethansulfonsäuregruppe im Molekül. Sie sind wasserlöslich und stellen hervorragende Vernetzungsmittel für gelatinehaltige Schichten dar.The curing agents (crosslinkers) of the invention contain at least 2 vinylsulfonyl groups and at least one sulfonethanesulfonic acid group in the molecule. They are water-soluble and are excellent cross-linking agents for gelatin-containing layers.

Die Verbindungen werden durch Umsetzung der Tris- und Polyvinylsulfone mit einem Mol Alkalibisulfit, oder, im Fall von Polyvinylsulfonen, mit 2 und mehr Molen Alkalibisulfit erhalten. Die Reaktion ist in Liebigs Annalen 601, 81 (1956) im Zusammenhang mit Monovinylsulfonen beschrieben, läßt sich aber ohne weiteres auf die obigen Verbindungen anwenden.The compounds are obtained by reacting the tris and polyvinyl sulfones with one mole of alkali bisulfite, or, in the case of polyvinyl sulfones, with 2 and more moles of alkali bisulfite. The reaction is described in Liebigs Annalen 601, 81 (1956) in connection with monovinyl sulfones, but can easily be applied to the above compounds.

Geeignete Ausgangsverbindungen für die Herstellung der erfindungsgemäßen Härtungs- oder Vernetzungsmittel sind Verbindungen der Formel

Figure imgb0002
in der

  • Z' einen x-wertigen aliphatischen Kohlenwasserstoffrest, der substituiert sein kann, einen x-wertigen, gegebenenfalls substituierten Cycloalkanrest oder einen, x-wertigen aromatischen Rest, der substituiert sein kann, bedeutet und
  • x für eine ganze Zahl von 3 bis 6 steht.
Suitable starting compounds for the preparation of the curing or crosslinking agents according to the invention are compounds of the formula
Figure imgb0002
 in the
  • Z 'is an x-valent aliphatic hydrocarbon radical which can be substituted, an x-valent, optionally substituted cycloalkane radical or an, x-valent aromatic radical which can be substituted, and
  • x represents an integer from 3 to 6.

Als Beispiele für Härtungsmittel gemäß der Erfindung seien folgende Verbindungen genannt:

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
 The following compounds may be mentioned as examples of curing agents according to the invention:
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024

Das Molverhältnis zwischen den Vinylsulfonverbindungen und Bisulfit kann in Abhängigkeit von der Angabe der Vinylsulfonylgruppen der Ausgangsverbindung, der Vinylsulfonverbindung, variieren. Wichtig ist nur, daß mindestens 2 Vinylsulfongruppen im Umsetzungsprodukt in ihrer ursprünglichen Form erhalten bleiben, weil nur so eine Vernetzungsreaktion mit den restlichen Gruppen der Gelatine möglich ist.The molar ratio between the vinyl sulfone compounds and bisulfite can vary depending on the indication of the vinyl sulfonyl groups of the starting compound, the vinyl sulfone compound. It is only important that at least 2 vinyl sulfone groups are retained in their original form in the reaction product, because this is the only way that a crosslinking reaction with the remaining groups of gelatin is possible.

Das Herstellungsverfahren der erfindungsgemäßen Härtungsmittel wird im folgenden anhand der Herstellung der Verbindungen 2, 3 und 19 erläutert. Alle anderen Verbindungen lassen sich in ähnlicher Weise herstellen.The production process of the curing agents according to the invention is explained below with reference to the preparation of compounds 2, 3 and 19. All other connections can be made in a similar manner.

Verbindung 2Connection 2 Anlagerung von NaHSO3 an die Verbindung C(CH2―SO2 ― CH = CH2)4 im Molverhältnis 1 : 1 führt zur VerbindungAddition of NaHSO 3 to the compound C (CH 2 ―SO 2 - CH = CH 2 ) 4 in a molar ratio of 1: 1 leads to the compound

Figure imgb0025
Figure imgb0025

Zu einer Lösung von 10,8g (0,025 Mol) der Verbindung C(CH2-S02-CH=CH2)4 in 300 ml Methylglykol tropft man bei 40°C die Lösung von 0,025 Mol (= 2,6 g) NaHS03 (40%ige wäßrige Lösung). Man läßt 12 Stunden bei Raumtemperatur stehen, dampft im Wasserstrahlvakuum ein und nimmt in 200 ml Aceton-Wasser 2 : 1 auf.The solution of 0.025 mol (= 2.6 g) NaHS0 is added dropwise at 40 ° C. to a solution of 10.8 g (0.025 mol) of the compound C (CH 2 -S0 2 -CH = CH 2 ) 4 in 300 ml of methyl glycol 3 (40% aqueous solution). The mixture is left to stand at room temperature for 12 hours, evaporated in a water jet vacuum and taken up 2: 1 in 200 ml of acetone-water.

Verbindung 19Connection 19 Anlagerung von NaHS03 an die Verbindung C(CH2―SO2―CH = CH2)4 im Molverhältnis 2 : 1 führt zur VerbindungAddition of NaHS0 3 to the compound C (CH 2 ―SO 2 ―CH = CH 2 ) 4 in a molar ratio of 2: 1 leads to the compound

Figure imgb0026
Figure imgb0026

Es wird wie vorher beschrieben gearbeitet, jedoch mit dem Unterschied, daß 0,05 Mol NaHS03 zugegeben werden. Das Produkt wird in 200 ml Aceton-Wasser 1 : 1 aufgenommen.The procedure is as described above, but with the difference that 0.05 mol of NaHS0 3 are added. The product is taken up 1: 1 in 200 ml acetone water.

Verbindung 3Connection 3

Figure imgb0027
Figure imgb0027

Zur Lösung von 17,8 g (0,05 Mol) der Verbindung

Figure imgb0028
in 300 ml Methylglykol tropft man bei 40° C 5,2 g (0,05 Mol) NaHS03 in Form einer 40%igen wäßrigen Lösung (13 g). Man hält 12 Stunden bei Raumtemperatur, engt bei einer Temperatur unter 40° C im Wasserstrahlvakuum ein und nimmt mit Wasser Aceton 2 1 (350 ml) auf.To dissolve 17.8 g (0.05 mol) of the compound
Figure imgb0028
 5.2 g (0.05 mol) of NaHS0 3 in the form of a 40% strength aqueous solution (13 g) are added dropwise at 40 ° C. in 300 ml of methyl glycol. The mixture is kept at room temperature for 12 hours, concentrated at a temperature below 40 ° C. in a water jet vacuum and taken up in water with acetone 2 l (350 ml).

Die erfindungsgemäßen Härtungsmittel können der Gießlösung entweder einige Zeit vor dem Beguß oder unmittelbar vor dem Beguß durch Dosierungseinrichtungen zugesetzt werden. Die Verbindungen können auch einer Überschichtungslösung zugesetzt werden, die nach Herstellung des fertigen Materials als Härtungsüberguß angewendet wird. Der fertige Schichtaufbau kann auch durch eine Lösung mit den erfindungsgemäßen Verbindungen gezogen werden und erhält dadurch die notwendige Menge Härtungsmittel zugeführt. Sämtliche bekannten Härtungsmittel können dabei für eine Vorhärtung des Materials eingesetzt werden. Schließlich lassen sich bei Mehrschichtenaufbauten, z. B. bei Colorfilmen und Colorpapieren, die erfindungsgemäßen Härtungsmittel durch Zusatz lediglich zu den Zwischenschichten in den Gesamtschichtaufbau einbringen. Dieses System hat deshalb Vorteile, weil die Gießlösungen für Zwischenschichten im allgemeinen weniger Gelatine enthalten und deshalb keine durch Viskositätsänderungen bedingter Probleme entstehen können.The hardening agents according to the invention can be added to the casting solution either some time before the casting or immediately before the casting by metering devices. The compounds can also be added to an overlay solution which is used as a curing overcoat after the finished material has been prepared. The finished layer structure can also be drawn through a solution with the compounds according to the invention and thereby receives the necessary amount of hardening agent. All known curing agents can be used for pre-curing the material. Finally, with multi-layer structures, e.g. B. in color films and color papers, the curing agents according to the invention by adding only to the intermediate layers in the overall layer structure. This system has advantages because the casting solutions for intermediate layers generally contain less gelatin and therefore no problems due to changes in viscosity can arise.

Die erfindungsgemäßen Härtungsmittel werden im allgemeinen in einer Menge von 0,01 bis 15 Gew.-% und vorzugsweise von 0,1 bis 10 Gew.-%, bezogen auf das Trockengewicht der Gelatine in der Beschichtungslösung, angewandt. Der Zeitpunkt der Zugabe zu der Beschichtungslösung ist nicht kritisch, Silberhalogenidemulsionen wird man dem Härter aber zweckmäßigerweise nach der chemischen Reifung zusetzen.The curing agents according to the invention are generally used in an amount of from 0.01 to 15% by weight and preferably from 0.1 to 10% by weight, based on the dry weight of the gelatin in the coating solution. The time of addition to the coating solution is not critical, but silver halide emulsions will expediently be added to the hardener after chemical ripening.

Unter photographischen Schichten sollen im vorliegenden Zusammenhang ganz allgemein Schichten verstanden werden, die im Rahmen photographischer Materialien Anwendung finden, beispielsweise lichtempfindliche Silberhalogenidemulsionsschichten, Schutzschichten, Filterschichten, Antihaloschichten, Rückschichten oder ganz allgemein photographische Hilfsschichten.In the present context, photographic layers are to be understood very generally as layers which are used in the context of photographic materials, for example light-sensitive silver halide emulsion layers, protective layers, filter layers, antihalo layers, backing layers or very generally photographic auxiliary layers.

Als lichtempfindliche Emulsionsschichten, für die das erfindungsgemäße Härtungsverfahren vorzüglich geeignet ist, seien beispielsweise solche Schichten genannt, denen nicht sensibilisierte Emulsionen, Röntgenemulsionen und andere spektral sensibilisierte Emulsionen zugrunde liegen. Weiter bewährt sich das Härtungsverfahren der Erfindung zur Härtung der für die verschiedenen photographischen Schwarz-Weiß- und Farbverfahren, wie Negativ-, Positiv- und Diffusionsübertragungsverfahren oder Druckverfahren verwendeten Gelatineschichten. Als besonders vorteilhaft hat sich das erfindungsgemäße Verfahren für die Härtung photographischer Schichtverbände erwiesen, die zur Durchführung farbphotographischer Prozesse bestimmt sind, z. B. solcher, die Emulsionsschichten mit Farbkupplern enthalten oder Emulsionsschichten, die zur Behandlung mit Lösungen bestimmt sind, welche Farbkuppler enthalten.As light-sensitive emulsion layers for which the curing method according to the invention is excellently suitable, there may be mentioned, for example, layers which are based on non-sensitized emulsions, X-ray emulsions and other spectrally sensitized emulsions. Furthermore, the hardening process of the invention has proven itself for hardening the gelatin layers used for the various black and white and color photographic processes, such as negative, positive and diffusion transfer processes or printing processes. The process according to the invention has proven to be particularly advantageous for the hardening of photographic layer dressings which are intended for carrying out color photographic processes, e.g. B. those that contain emulsion layers with color couplers or emulsion layers that are intended for treatment with solutions containing color couplers.

Die Wirkung der in erfindungsgemäßer Weise angewandten Verbindungen wird durch die üblichen photographischen Zusätze nicht beeinträchtigt. Ebenso sind die Härtungsmittel indifferent gegenüber photographisch wirksamen Substanzen, wie z. B. wasserlöslichen und emulgierten wasserunlöslichen Farbkomponenten, Stabilisatoren, Sensibilisatoren. Sie üben ferner keinen nachteiligen Einfluß auf die lichtempfindlichen Silberhalogenidemulsionen aus.The effect of the compounds used in the manner according to the invention is not impaired by the usual photographic additives. Likewise, the hardeners are indifferent to photographically active substances, such as. B. water-soluble and emulsified water-insoluble color components, stabilizers, sensitizers. Furthermore, they have no adverse effect on the light-sensitive silver halide emulsions.

Als lichtempfindliche Bestandteile können die Emulsionsschichten bekannte Silberhalogenide, wie Silberchlorid, Silberjodid, Silberbromid, Silberjodbromid, Silberchlorbromid oder Silberchlorjodbromid enthalten. Die Emulsionen können durch Edelmetallverbindungen chemisch sensibilisiert werden, z. B. durch Verbindungen von Ruthenium, Rhodium, Palladium, Iridium, Platin, Gold und dergleichen, wie Ammoniumchlorpalladat, Kaliumchloroplatinat, Kaliumchlorpalladinat, oder Kaliurnthloroaurat. Sie können ferner spezielle Sensibilisierungsmittel von z. B. Schwefelverbindungen, Zinn(11)salze, Polyamine oder Polyalkylenoxidverbindungen enthalten. Weiterhin können die Emulsionen mit dem hierfür üblichen Farbstoffen, von z. B. mit Cyaninfarbstoffen, Merocyaninfarbstoffen und Mischcyaninfarbstoffen optisch sensibilisiert werden.The emulsion layers can contain known silver halides as light-sensitive components, such as silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide or silver chlorobiodobromide. The emulsions can be chemically sensitized by precious metal compounds, e.g. B. by compounds of ruthenium, rhodium, palladium, iridium, platinum, gold and the like, such as ammonium chloropalladate, potassium chloroplatinate, potassium chloropalladinate, or potassium thloroaurate. You can also use special sensitizers such. B. sulfur compounds, tin (11) salts, Contain polyamines or polyalkylene oxide compounds. Furthermore, the emulsions with the usual dyes, for. B. optically sensitized with cyanine dyes, merocyanine dyes and mixed cyanine dyes.

Die Emulsionen können schließlich alle bekannten Kuppler, z. B. farblose Kuppler oder farbige Kuppler, Stabilisatoren, wie Quecksilberverbindungen, Triazolverbindungen, Azaindenverbindungen, Benzothiazoliumverbindungen oder Zinkverbindungen, Netzmittel, wie Dihydroxyalkane, die Filmbildungseigenschaften verbessernde Mittel, z. B. die bei der Emulsionspolymerisation von Alkylacrylat- oder Alkylmethacrylat/Acrylsäure- oder Methacrylsäuregemischpolymeren erhalten, in Wasser dispergierbaren, teilchenförmigen Hochpolymeren, Styrol/Maleinsäure-Mischpolymere oder Styrol/Maleinsäureanhydrid-halbalkylester-Mischpolymere, Beschichtungshilfsmittel, wie Polyethylenglykollaurylether, sowie andere übliche photographische Hilfsmittel, enthalten.The emulsions can finally all known couplers, for. B. colorless couplers or colored couplers, stabilizers such as mercury compounds, triazole compounds, azainden compounds, benzothiazolium compounds or zinc compounds, wetting agents such as dihydroxyalkanes, the film-forming properties improving agents, for. B. obtained in the emulsion polymerization of alkyl acrylate or alkyl methacrylate / acrylic acid or methacrylic acid mixed polymers, water-dispersible, particulate high polymers, styrene / maleic acid mixed polymers or styrene / maleic anhydride-semi-alkyl ester mixed polymers, coating auxiliaries, such as polyethylene glycol, as well as other photographic assistants, conventional photographic ether contain.

Bemerkenswert ist, daß die Härtungsmittel der Erfindung, wenn sie in farbphotographischen Materialien angewendet werden, die Kuppler, wie z. B. Purpurkuppler vom 5-Pyrazolontyp, Blaugrünkuppler vom Naphthol- oder Phenol-Typ und Gelbkuppler vom offenkettigen Ketomethylen-Typ, sogenannte 2-Äqivalent- und 4-Äqivalenten Kuppler, die von den obengenannten Kupplern abgeleitet sind, und sogenannte maskierende Kuppler mit einer Arylazogruppe an der aktiven Stelle enthalten, keine Farbveränderungen in den photographischen Materialien auftreten.It is noteworthy that the curing agents of the invention, when used in color photographic materials, the couplers, such as. B. purple couplers of the 5-pyrazolone type, cyan couplers of the naphthol or phenol type and yellow couplers of the open-chain ketomethylene type, so-called 2-equivalent and 4-equivalent couplers, which are derived from the above-mentioned couplers, and so-called masking couplers with an arylazo group contained in the active site, no color changes occur in the photographic materials.

Die Härtungsmittel der Erfindung zeichnen sich den bekannten Härtern vom Vinylsulfonyl-Typ gegenüber dadurch aus, daß sie weder eine unmittelbar einsetzende Härtung noch eine sogenannte Uberhärtung der mit ihnen behandelten photographischen Schichten bewirken, was einerseits für das Herstellungsverfahren und andererseits für die Lagerung photographischer Materialien einen Vorteil darstellt.The hardening agents of the invention are distinguished from the known hardeners of the vinylsulfonyl type in that they cause neither immediate hardening nor so-called over-hardening of the photographic layers treated with them, which is an advantage for the production process and for the storage of photographic materials represents.

Die Vernetzung des photographischen Materials wird mit Hilfe des Schmelzpunktes der Schichten bestimmt, der sich wie folgt ermitteln läßt:

  • Der auf eine Unterlage vergossene Schichtverband wird zur Hälfte in Wasser getaucht, das kontinuierlich bis 100°C erwärmt wird. Die Temperatur, bei der die Schicht von der Unterlage abläuft (Schlierenbildung), wird als Schmelzpunkt bzw. Abschmelzpunkt bezeichnet. Nach diesem Verfahren zeigen ungehärtete Proteinschichten in keinem Falle eine Schmelzpunkterhöhung. Der Abschmelzpunkt liegt unter diesen Bedingungen bei 30 bis 35° C.
The crosslinking of the photographic material is determined using the melting point of the layers, which can be determined as follows:
  • Half of the layered compound cast on a base is immersed in water, which is continuously heated to 100 ° C. The temperature at which the layer runs off the substrate (streak formation) is referred to as the melting point or melting point. According to this process, uncured protein layers never show an increase in melting point. The melting point is 30 to 35 ° C under these conditions.

Zur Bestimmung der Wasseraufnahme wird der Prüfling in einem herkömmlichen Farbentwicklungsprozeß als Schwarzblatt entwickelt und nach dem Schlußbad nach Abstreifen des überschüssigen Wassers gewogen. Dann wird die Probe getrocknet und erneut gewogen. Die Differenz ergibt, von der Fläche des Prüflings auf 1 m2 umgerechnet, die Wasseraufnahme pro m2.To determine the water absorption, the test specimen is developed as a black sheet in a conventional color development process and weighed after the final bath after the excess water has been stripped off. The sample is then dried and weighed again. The difference, converted from the area of the test specimen to 1 m 2 , gives the water absorption per m 2 .

Die Quellung wird nach 10 Minuten Behandlung eines Probestreifens in destilliertem Wasser bei 22° C gravimetrisch gemessen. Sie wird durch den Quellfaktor charakterisiert:

Figure imgb0029
The swelling is measured gravimetrically after treatment of a test strip in distilled water at 22 ° C. for 10 minutes. It is characterized by the swelling factor:
Figure imgb0029

Zur Bestimmung der Naßkratzfestigkeit wird eine Metallspitze definierter Größe über die nasse Schicht geführt und mit zunehmendem Gewicht belastet. Die Naßkratzfestigkeit wird durch das Gewicht angegeben, bei dem die Spitze eine sichtbare Kratzspur auf der Schicht hinterläßt. Ein hohes Gewicht entspricht einer hohen Naßkratzfestigkeit.To determine the wet scratch resistance, a metal tip of a defined size is passed over the wet layer and loaded with increasing weight. The wet scratch resistance is indicated by the weight at which the tip leaves a visible scratch mark on the layer. A high weight corresponds to a high wet scratch resistance.

Beispiel 1example 1

Zu 100 ml einer gießfertigen photographischen Silberbromid-Gelatine-Emulsion, die 10 Gew.-% Gelatine, enthält, werden bei pH 6,2 jeweils 1 und 2 g der erfindungsgemäßen Verbindungen, bezogen auf 100 g Gelatine, in Form einer wäßrigen Lösung zugegeben. Die Mischung wird gut gerührt und sofort mit einer üblichen Gießmaschine auf eine präparierte Cellulosetriacetatunterlage gegossen und getrocknet.1 and 2 g of the compounds according to the invention, based on 100 g of gelatin, in the form of an aqueous solution, are added at pH 6.2 to 100 ml of a ready-to-pour photographic silver bromide gelatin emulsion which contains 10% by weight gelatin. The mixture is stirred well and immediately poured onto a prepared cellulose triacetate base using a conventional casting machine and dried.

Das Material wird unter verschiedenen Klimabedingungen gelagert und anschließend wird die Vernetzung durch Bestimmung des Schichtschmelzpunktes, der Naßkratzfestigkeit und des Quellfaktors geprüft. Eine gute Vernetzung gibt sich durch einen hohen Schichtschmelzpunkt, eine hohe Naßkratzfestigkeit und einen niedrigen Quellfaktor zu erkennen.The material is stored under various climatic conditions and then the crosslinking is checked by determining the layer melting point, the wet scratch resistance and the swelling factor. Good crosslinking is evident from a high layer melting point, high wet scratch resistance and a low swelling factor.

Die Ergebnisse sind in der folgenden Tabelle zusammengestellt.

Figure imgb0030
The results are summarized in the following table.
Figure imgb0030

Die Tabelle 1 zeigt, daß man kochfeste Schichten (Schmelzpunkt 100° C) bereits bei Zusatz von 1 bis 2 g Härter pro 100 g Gelatine erhält. Nach Lagerung bei 36°C und 80% rel. Luftfeuchtigkeit nimmt die Härtung in gemäßigter Form zu und man erhält keine Überhärtung. Die Gießlösungen können 1 Stunde ohne Viskositätserhöhungen stehen gelassen werden, ein Zeichen für die vorteilhafte geringe Vemetzung der Gelatine in der Lösung. Die Schichten zeigten gegenüber der ungehärteten Schicht nach der Entwicklung und Fixierung keine nachteiligen Eigenschaften. Empfindlichkeit, Schleierwerte und y-Werte veränderten sich nicht. Die Härtungsmittel verhielten sich gegenüber der Halogensilberemulsion auch nach längerer Lagerung der Schichten inert.Table 1 shows that boil-resistant layers (melting point 100 ° C.) are obtained with the addition of 1 to 2 g hardener per 100 g gelatin. After storage at 36 ° C and 80% rel. Humidity increases the hardening in a moderate form and no over-hardening is obtained. The casting solutions can be left for 1 hour without increasing the viscosity, a sign of the advantageous low crosslinking of the gelatin in the solution. The layers showed no disadvantageous properties compared to the uncured layer after development and fixing. Sensitivity, fog values and y values did not change. The hardeners remained inert towards the halosilver emulsion even after the layers had been stored for a long time.

Beispiel 2Example 2

Ein Farbaufsichtsmaterial wird hergestellt, indem man auf eine mit Polyethylen kaschierte und mit einer Haftschicht versehene Papierunterlage nacheinander folgende Schichten aufträgt, wobei die Emulsionsschichten die üblichen Zusätze an Netzmittel, Stabilisatoren usw. enthalten:

  • 1. Als Unterguß eine 4 µm dicke blauempfindliche Silberbromidemulsionsschicht, die pro kg Emulsion 25,4 g Silber (88% AgBr, 12% AgCI), 80 g Gelatine und 34 g der Gelbkomponente
    Figure imgb0031
    enthält,
  • 2. als Zwischenschicht eine 1 µm dicke Gelatineschicht,
  • 3. als Mittelguß eine 4 µm dicke grünempfindliche Silberchloridbromidemulsionsschicht, die pro kg Emulsion 22 g Silber (77% AgCI, 23 % AgBr), 80 g Gelatine und 13 g der Purpurkomponente
    Figure imgb0032
    enthält,
  • 4. eine 1 µm dicke Zwischenschicht wie unter 2. angegeben,
  • 5. als Oberguß eine 4 µm dicke rotempfindliche Silberchloridbromidemulsionsschicht, die pro kg Emulsion 23 g Silber (80 % AgCI, 20 % AgBr), 80 g Gelatine und 15,6 g der Blaugrünkomponente
    Figure imgb0033
    enthält,
  • 6. eine um dicke Schutzschicht aus
    Figure imgb0034
A color control material is produced by successively applying the following layers onto a paper base laminated with polyethylene and provided with an adhesive layer, the emulsion layers containing the usual additions of wetting agents, stabilizers, etc.:
  • 1. As a base, a 4 µm thick blue-sensitive silver bromide emulsion layer containing 25.4 g of silver (88% AgBr, 12% AgCI), 80 g of gelatin and 34 g of the yellow component per kg of emulsion
    Figure imgb0031
     contains
  • 2. a 1 µm thick gelatin layer as an intermediate layer,
  • 3. as a center casting, a 4 μm thick green-sensitive silver chloride bromide emulsion layer containing 22 g of silver (77% AgCl, 23% AgBr), 80 g of gelatin and 13 g of the purple component per kg of emulsion
    Figure imgb0032
     contains
  • 4. a 1 µm thick intermediate layer as indicated under 2.,
  • 5. as a top casting, a 4 μm thick red-sensitive silver chloride bromide emulsion layer containing 23 g of silver (80% AgCl, 20% AgBr), 80 g of gelatin and 15.6 g of the cyan component per kg of emulsion
    Figure imgb0033
     contains
  • 6. a thick protective layer
    Figure imgb0034

Zu jeder Gießlösung wurden, bezogen auf Gelatine, 3,5 g Härtungsmittel auf 100 g Gelatine zugesetzt und der Schichtaufbau durchgeführt (Versuchsreihe 1). In einer 2. Versuchsreihe wurden die Härtungsmittel nur in die Zwischenschichten gegeben und zwar in einer solchen Menge, daß in dem genannten Schichtverband wieder 3,5 g Härtungsmittel, bezogen auf 100 g Gelatine, vorhanden war. Beide Reihen wurden unter gleichen Bedingungen geiagert und auf Härtung bzw. Vernetzung untersucht. Der pH-Wert der Gießlösung lag stets bei pH 6,5.

Figure imgb0035
Based on gelatin, 3.5 g hardening agent per 100 g gelatin were added to each casting solution and the layer structure was carried out (test series 1). In a second series of experiments, the hardening agents were only added to the intermediate layers in such an amount that 3.5 g of hardening agent, based on 100 g of gelatin, was again present in the layer structure mentioned. Both series were grown under the same conditions and examined for hardening or crosslinking. The pH of the casting solution was always pH 6.5.
Figure imgb0035

Aus den ungefähr gleichen Werten für die Vernetzung der Schichten der Versuchsreihen 1 und 2 ergibt sich, daß das Härtungsmittel sehr gut diffundiert und selbst in den Schichten eine gute Härtungswirkung aufweist, in die es erst eindiffundieren muß. Es zeigt sich sogar die Tendenz, daß die Gesamthärtung besser ist, wenn das Härtungsmittel nicht in alle Schichten dosiert wird, sondern nur in die Zwischenschichten. Nach der farbphotographischen Verarbeitung in den üblichen Verarbeitungsbädern wurden Schichten mit vergleichbaren photographischen Werten, wie Empfindlichkeit, Schleier und Gradation erhalten. Beide Härtungsmittel verhalten sich in beiden Anwendungsformen gegenüber derfarbphotograpischen Emulsion und den Farbkupplerverbindungen inert.From the approximately the same values for the crosslinking of the layers of test series 1 and 2, it follows that the hardening agent diffuses very well and has a good hardening effect even in the layers into which it first has to diffuse. There is even a tendency that the overall hardening is better if the hardening agent is not dosed in all layers, but only in the intermediate layers. After color photographic processing in the usual processing baths, layers with comparable photographic values such as sensitivity, fog and gradation were obtained. In both application forms, both hardening agents are inert towards the color photographic emulsion and the color coupler compounds.

Beispiel 3Example 3

Auf einen mit einer Haftschicht versehenen Cellulosetriacetat-Schichtträger werden nacheinander folgende Schichten aufgetragen:

  • 1. Eine Lichthofschutzschicht, die pro m24 g Gelatine und 0,7 g kolloidales schwarzes Silber enthält,
  • 2. eine 6 µm dicke rotempfindliche Schicht, die pro m2 35 mMol Silberhalogenid (95% AgBr, 5% AgJ), 4 mMol eines Blaugrünkupplers der Formel
    Figure imgb0036
    und 6 g Gelatine enthält,
  • 3. eine 0,5 µm dicke Gelatinezwischenschicht,
  • 4. eine 6 µm dicke grünempfindliche Schicht, die der des Beispiels 1 entspricht, die als Purpurkuppler die Verbindung
    Figure imgb0037
    enthält,
  • 5. eine 0,5 µm dicke Gelatinezwischenschicht,
  • 6. eine Gelbfilterschicht, die pro m21,5 g Gelatine und 0,2 g kolloidales gelbes Silber enthält,
  • 7. eine 6 µm dicke blauempfindliche Schicht, die pro m2 13 mMol Silberhalogenid (95% AgBr, 5% AgJ), 2 mMol eines Gelbkupplers der Formel
    Figure imgb0038
    und 5 g Gelatine enthält und
  • 8. eine 1 µm dicke Gelatineschutzschicht.
The following layers are applied in succession to a cellulose triacetate layer support provided with an adhesive layer:
  • 1. An antihalation layer which contains 4 g of gelatin and 0.7 g of colloidal black silver per m 2 ,
  • 2. a 6 μm thick red-sensitive layer containing 35 mmol silver halide (95% AgBr, 5% AgJ), 4 mmol of a cyan coupler of the formula per m 2
    Figure imgb0036
     and contains 6 g of gelatin,
  • 3. a 0.5 µm thick gelatin intermediate layer,
  • 4. a 6 micron thick green-sensitive layer, which corresponds to that of Example 1, the connection as a purple coupler
    Figure imgb0037
     contains
  • 5. a 0.5 µm thick gelatin intermediate layer,
  • 6. a yellow filter layer which contains 21.5 g of gelatin and 0.2 g of colloidal yellow silver per m,
  • 7. a 6 μm thick blue-sensitive layer containing 13 mmol silver halide (95% AgBr, 5% AgJ), 2 mmol of a yellow coupler of the formula per m 2
    Figure imgb0038
     and 5 g of gelatin and
  • 8. a 1 µm thick gelatin protective layer.

Der Schichtverband wird danach getrocknet.The layered structure is then dried.

Die Schichten haben nach der Trocknung einen Schichtschmelzpunkt von 38° C und waren wegen der hohen Quellung und der starken Neigung zur Runzelkornbildung auch in Bädern bei 20° C nicht verarbeitbar.After drying, the layers had a layer melting point of 38 ° C and, due to the high swelling and the strong tendency to form wrinkles, could not be processed in baths at 20 ° C.

Auf Proben des Materials wurde nach der Trocknung jeweils ein Härtungsmittelguß aufgetragen:

  • Härtungsmittelübergußlösung 1:
    • 0,025 Mol Verbindung 3 auf 200 ccm wäßrige Lösung. Die Lösung enthielt außerdem 0,375 Gew.-% Saponin.
  • Härtungsmittelübergußlösung II:
    • 0,025 Mol Verbindung 2 auf 200 ccm wäßrige Lösung. Die Lösung enthielt außerdem 0,375 Gew.-% Saponin.
A hardening agent cast was applied to samples of the material after drying:
  • Hardener pouring solution 1:
    • 0.025 mol of compound 3 per 200 cc aqueous solution. The solution also contained 0.375% by weight of saponin.
  • Hardener pouring solution II:
    • 0.025 mol of compound 2 per 200 cc aqueous solution. The solution also contained 0.375% by weight of saponin.

Nach der Trocknung und nach Lagerung des Aufbaus war der gesamte Schichtverband gehärtet. Die folgenden Ergebnisse wurden erhalten:

Figure imgb0039
After drying and after storing the structure, the entire layer structure was hardened. The following results were obtained:
Figure imgb0039

Die Meßwerte zeigen, daß das Härtungsmittel den gesamten Schichtverband durchwandert und gehärtet hat. Die photographischen Werte wie Empfindlichkeit und Schleier wurden nicht verändert.The measured values show that the hardening agent has migrated through the entire layer structure and hardened. The photographic values such as sensitivity and fog were not changed.

Claims (16)

1. Process for hardening a photographic material with a compound containing vinyl sulphonyl groups as cross-linking agent, characterised in that a bisulphite addition product, containing at least two free vinyl sulphonyl groups in the molecule, of a compound containing up to 6 vinyl sulphonyl groups is used as cross-linking agent.
2. Process according to claim 1, characterised in that the cross-linking agent used is a compound of the general formula
Figure imgb0050
in which
Z denotes an x-functional, optionally substituted aliphatic hydrocarbon radical, an x-functional, optionally substituted cycloalkane radical, an x-functional, optionally substituted hexahydro triazine radical or an x-functional, optionally substituted, aromatic radical,
x denotes an integer of from 3 to 6,
a denotesx-b,
b denotes 1 or 2 and
Me denotes an alkali metal ion or an ammonium ion.
3. Process according to claims 1 and 2, characterised in that the cross-linking agent used is the compound
Figure imgb0051
4. Process according to claims 1 and 2, characterised in that the cross-linking agent used is the compound
Figure imgb0052
5. Process according to claims 1 and 2, characterised in that the cross-linking agent used is the compound
Figure imgb0053
6. Process according to claims 1 and 2, characterised in that the cross-linking agent used is the compound
Figure imgb0054
7. Process according to claims 1 to 6, characterised in that the bisulphite addition product is used in a quantity of 0 1 to 10% by weight, based on the binder to be hardened in the photographic material.
8. Process according to claims 1 to 7, characterised in that a colour photographic multilayer material is hardened.
9. Photosensitive photographic silver halide material constisting of a support layer and, applied thereto, at least one gelatin-containing layer hardened with a compound containing vinyl sulphonyl groups, characterised in that the hardening compound is a bisulphite addition product, containing at least two free vinyl sulphonyl groups in the molecule, of a compound containing up to 6 vinyl sulphonyl groups.
10. Photosensitive material according to claim 9, characterised in that the hardening compound corresponds to the general formula
Figure imgb0055
wherein
Z denotes an x-functional, optionally substituted aliphatic hydrocarbon radical, an x-functional, optionally substituted, cycloalkane radical or an x-functional, optionally substituted, aromatic radical,
x denotes an integer of from 3 to 6,
a denotesx-b,
b denotes 1 or 2 and
Me denotes an alkali metalion or an ammonium ion.
11. Photosensitive material according to claims 9 and 10, characterised in that it is hardened with the compound
Figure imgb0056
12. Photosensitive material according to claims 9 and 10, characterised in that it is hardened with the compound
Figure imgb0057
13. Photosensitive material according to claims 9 and 10, characterised in that it is hardened with the compound
Figure imgb0058
14. Photosensitive material according to claims 9 and 10, characterised in that it is hardened with the compound
Figure imgb0059
15. Photosensitive material according to claims 9 to 14, characterised in that it contains 0.1 to 10% by weight of the hardening compound, based on the dry weight of the gelatin.
16. Photosensitive material according to claims 9 to 15, characterised in that it is a colour photographic multilayer material.
EP80106380A 1979-10-30 1980-10-20 Method for hardening a photographic material, and photosensitive material Expired EP0029127B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2943807 1979-10-30
DE19792943807 DE2943807A1 (en) 1979-10-30 1979-10-30 METHOD FOR CURING A PHOTOGRAPHIC MATERIAL

Publications (2)

Publication Number Publication Date
EP0029127A1 EP0029127A1 (en) 1981-05-27
EP0029127B1 true EP0029127B1 (en) 1982-05-12

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EP (1) EP0029127B1 (en)
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DE (2) DE2943807A1 (en)

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Publication number Priority date Publication date Assignee Title
DE3224983A1 (en) * 1982-07-03 1984-01-05 Agfa-Gevaert Ag, 5090 Leverkusen METHOD FOR CURING PHOTOGRAPHIC GELATINS WITH VINYL SULPHONES CONTAINING SULFONYL ETHYL SULFATE GROUPS
DE3628717A1 (en) * 1986-08-23 1988-02-25 Agfa Gevaert Ag HARDENER FOR PROTEINS, A HARDENED BINDER LAYER AND A PHOTOGRAPHIC RECORDING MATERIAL CONTAINING SUCH A LAYER
DE3708541A1 (en) * 1987-03-17 1988-10-13 Agfa Gevaert Ag HARDENER FOR PROTEINS, A HARDENED BINDER LAYER AND A PHOTOGRAPHIC RECORDING MATERIAL CONTAINING SUCH A LAYER
JPS63241539A (en) * 1987-03-30 1988-10-06 Fuji Photo Film Co Ltd Process for hardening gelatin
JP2528344B2 (en) * 1988-02-10 1996-08-28 富士写真フイルム株式会社 Silver halide color photographic light-sensitive material
US5187259A (en) * 1990-11-14 1993-02-16 Eastman Kodak Company Chain extended gelatin
US5411856A (en) * 1994-01-10 1995-05-02 Eastman Kodak Company Carbamyl-substituted bis(vinylsulfonyl) methane hardeners
DE19938508A1 (en) 1999-08-13 2001-02-15 Agfa Gevaert Ag A gelatin containing silver halide material, useful in color film and copying, comprises a light sensitive silver halide emulsion layer containing a 3-benzyl substituted-2-coumaranone compound.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE576882A (en) * 1958-03-19
US3615622A (en) * 1965-08-16 1971-10-26 Fuji Photo Film Co Ltd Hardening gelatin with polymeric-bisulfite addition product
DE1622260A1 (en) * 1968-02-16 1969-11-27 Agfa Gevaert Ag Process for curing photographic layers containing gelatin
DE2002063A1 (en) * 1970-01-17 1971-10-07 Agfa Gevaert Ag Process for curing photographic layers containing gelatin
US4088495A (en) * 1974-10-14 1978-05-09 Konishiroku Photo Industry Co., Ltd. Silver halide photographic element containing a gelatinous layer hardened with an aliphatic hydrocarbon having at least three vinylsulfonyl groups
US4142897A (en) * 1975-08-09 1979-03-06 Konishiroku Photo Industry Co., Ltd. Gelatino silver halide photographic material hardened with a reaction product of a vinylsulfonyl compound and a water soluble compound
JPS5221059A (en) * 1975-08-09 1977-02-17 Konishiroku Photo Ind Co Ltd Method for hardening gelatin
JPS5357257A (en) * 1976-11-04 1978-05-24 Fuji Photo Film Co Ltd Setting of gelatin
US4161407A (en) * 1977-10-06 1979-07-17 Eastman Kodak Company Crosslinkable polymers having vinylsulfonyl groups or styrylsulfonyl groups and their use as hardeners for gelatin

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EP0029127A1 (en) 1981-05-27
US4323646A (en) 1982-04-06
DE2943807A1 (en) 1981-05-14
DE3060420D1 (en) 1982-07-01

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