EP0029127B1 - Procédé de durcissement d'un matériau photographique et matériau photosensible - Google Patents

Procédé de durcissement d'un matériau photographique et matériau photosensible 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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Prior art keywords
compound
hardening
photographic
denotes
hardened
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EP80106380A
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German (de)
English (en)
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EP0029127A1 (fr
Inventor
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.

Claims (16)

1. Procédé de durcissement d'un élément photographique avec un composé contenant des groupes vinylsulfonyle comme agent de réticulation, caractérisé en ce que, comme agent de réticulation, on utilise un produit d'addition de bisulfite (dont la molécule contient au moins deux groupes vinylsulfonyle libres) d'un composé contenant jusqu'à six groupes vinylsulfonyle.
2. Procédé suivant la revendication 1, caractérisé en ce que, comme agent de réticulation, on utilise un composé de formule générale:
Figure imgb0060
dans laquelle:
Z représente un radical d'hydrocarbure aliphatique x-valent éventuellement substitué, un radical cycloalcane x-valent éventuellement substitué, un radical d'hexahydrotriazine x-valent éventuellement substitué ou un radical aromatique x-valent éventuellement substitué,
x représente un nombre entier de 3 à 6,
a représente x―b,
b représente 1 ou 2, et
Me représente un ion d'un métal alcalin ou d'ammonium.
3. Procédé suivant les revendications 1 et 2, caractérisé en ce que, comme agent de réticulation, on utilise le composé de formule:
Figure imgb0061
4. Procédé suivant les revendications 1 et 2, caractérisé en ce que, comme agent de réticulation, on utilise le composé de formule:
Figure imgb0062
5. Procédé suivant les revendications 1 et 2, caractérisé en ce que, comme agent de réticulation, on utilise le composé de formule:
Figure imgb0063
6. Procédé suivant les revendications 1 et 2, caractérisé en ce que, comme agent de réticulation, on utilise le composé de formule:
Figure imgb0064
7. Procédé suivant les revendications 1 à 6, caractérisé en ce qu'on utilise le produit d'addition de bisulfite en une quantité de 0,1 à 10% en poids, calculé sur l'agent liant à durcir de l'élément photographique.
8. Procédé suivant les revendications 1 à 7, caractérisé en ce qu'on durcit un élément à plusieurs couches pour la photographie en couleurs.
9. Elément photographique photosensible à l'halogénure d'argent constitué d'un support de couches sur lequel est appliquée au moins une couche contenant de la gélatine et durcie avec un composé contenant des groupes vinylsulfonyle, caractérisé en ce que le composé durcissant est un produit d'addition de bisulfite (dont la molécule contient au moins deux groupes vinylsulfonyle libres) d'un composé contenant jusqu'à six groupes vinylsulfonyle.
10. Elément photosensible suivant la revendication 9, caractérisé en ce que le composé durcissant répond à la formule générale:
Figure imgb0065
dans laquelle:
Z représente un radical d'hydrocarbure aliphatique x-valent éventuellement substitué, un radical cycloalcane x-valent éventuellement substitué ou un radical aromatique x-valent éventuellement substitué,
x représente un nombre entier de 3 à 6,
a représente x - b,
b représente 1 ou 2, et
Me représente un ion d'un métal alcalin ou d'ammonium.
11. Elément photosensible suivant les revendications 9 et 10, caractérisé en ce qu'on le durcit avec le composé de formule:
Figure imgb0066
12. Elément photosensible suivant les revendications 9 et 10, caractérisé en ce qu'on le durcit avec le composé de formule:
Figure imgb0067
13. Elément photosensible suivant les revendications 9 et 10, caractérisé en ce qu'on le durcit avec le composé de formule:
Figure imgb0068
14. Elément photosensible suivant les revendications 9 et 10, caractérisé en ce qu'on le durcit avec le compose de formule:
Figure imgb0069
15. Elément photosensible suivant les revendications 9 à 14, caractérisé en ce qu'il contient 0,1 à 10% en poids du composé durcissant, calculé sur le poids sec de la gélatine.
16. Elément photosensible suivant les revendications 9 à 15, caractérisé en ce qu'il est un élément à plusieurs couches pour la photographie en couleurs.
EP80106380A 1979-10-30 1980-10-20 Procédé de durcissement d'un matériau photographique et matériau photosensible Expired EP0029127B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792943807 DE2943807A1 (de) 1979-10-30 1979-10-30 Verfahren zur haertung eines photographischen materials
DE2943807 1979-10-30

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EP0029127A1 EP0029127A1 (fr) 1981-05-27
EP0029127B1 true EP0029127B1 (fr) 1982-05-12

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US (1) US4323646A (fr)
EP (1) EP0029127B1 (fr)
CA (1) CA1146792A (fr)
DE (2) DE2943807A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3224983A1 (de) * 1982-07-03 1984-01-05 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur haertung photographischer gelatine mit sulfonyl-ethylsulfatgruppenhaltigen vinylsulfonen
DE3628717A1 (de) * 1986-08-23 1988-02-25 Agfa Gevaert Ag Haertungsmittel fuer proteine, eine damit gehaertete bindemittelschicht und eine solche schicht enthaltendes fotografisches aufzeichnungsmaterial
DE3708541A1 (de) * 1987-03-17 1988-10-13 Agfa Gevaert Ag Haertungsmittel fuer proteine, eine damit gehaertete bindemittelschicht und ein eine solche schicht enthaltendes fotografisches aufzeichnungsmaterial
JPS63241539A (ja) * 1987-03-30 1988-10-06 Fuji Photo Film Co Ltd ゼラチンの硬化方法
JP2528344B2 (ja) * 1988-02-10 1996-08-28 富士写真フイルム株式会社 ハロゲン化銀カラ―写真感光材料
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 (de) 1999-08-13 2001-02-15 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE576882A (fr) * 1958-03-19
US3615622A (en) * 1965-08-16 1971-10-26 Fuji Photo Film Co Ltd Hardening gelatin with polymeric-bisulfite addition product
DE1622260A1 (de) * 1968-02-16 1969-11-27 Agfa Gevaert Ag Verfahren zur Haertung von photographischen,gelatinehaltigen Schichten
DE2002063A1 (de) * 1970-01-17 1971-10-07 Agfa Gevaert Ag Verfahren zur Haertung von photographischen gelatinehaltigen Schichten
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

Also Published As

Publication number Publication date
EP0029127A1 (fr) 1981-05-27
DE2943807A1 (de) 1981-05-14
DE3060420D1 (en) 1982-07-01
CA1146792A (fr) 1983-05-24
US4323646A (en) 1982-04-06

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