EP0237887B1 - Procéde de préparation d'un matériau d'enregistrement photographique - Google Patents

Procéde de préparation d'un matériau d'enregistrement photographique Download PDF

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Publication number
EP0237887B1
EP0237887B1 EP87103219A EP87103219A EP0237887B1 EP 0237887 B1 EP0237887 B1 EP 0237887B1 EP 87103219 A EP87103219 A EP 87103219A EP 87103219 A EP87103219 A EP 87103219A EP 0237887 B1 EP0237887 B1 EP 0237887B1
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EP
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Prior art keywords
group
color
layer
binder
hardener
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EP87103219A
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German (de)
English (en)
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EP0237887A2 (fr
EP0237887A3 (en
Inventor
Erich Dr. Wolff
Hans Dr. Langen
Wolfgang Dr. Himmelmann
Günter Dr. Helling
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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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
    • 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 method for producing a photographic recording material with at least one hardened silver halide emulsion layer containing a proteinaceous binder, in particular gelatin, which is protected by special additives against the damaging influence of formaldehyde.
  • Photographic recording materials usually consist of a support and light-sensitive gelatin-containing silver halide emulsion layers and optionally non-light-sensitive auxiliary layers which also contain gelatin.
  • the light-sensitive silver halide gelatin emulsion layers of color photographic recording materials contain the color components required to form the image dyes in the three primary colors.
  • the multi-layered recording materials mentioned here in black and white and color photography and their production are generally known and are described, for example, in the "Photography” chapter in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18.
  • crosslinking agents which are also called hardeners.
  • Both inorganic and organic photographically inert compounds which can crosslink the gelatin via the carboxyl groups and / or the amino groups are suitable as hardening agents.
  • curing agents are aldehydes, e.g. B. formaldehyde, glyoxal, glutaraldehyde, aldehyde acids, e.g. B. mucochloric acid, diketones, e.g. B. diacetyl, dihalides, e.g.
  • 1,3-dichloropropanol bis-vinyl sulfone compounds, diisocyanate bisulfite compounds, bis-epoxides, bis-aziridines, peptide reagents such as carbodiimides, N-carbamoylpyridinium and isoxazolium salts or substituted 2,4-dichlorotriazines, e.g. N, N ', N' '- called trisacryloyl-perhydro-s-triazine.
  • aldehydes such as glyoxal, glutaraldehyde, succinaldehyde and in particular formaldehyde
  • curing agents are associated with certain difficulties.
  • These aldehydes can not only cause crosslinking of the gelatin layers that is difficult to limit; for example, they can also impair the functionality of the color components which may be present in the layers, and they can give rise to fog. For this reason, other hardeners are usually preferred to aldehydes in practice.
  • the disadvantageous effect described can also be expected if the aldehydes are used in the photographic recording materials have not been specifically incorporated, but only penetrate the photographic layers, for example, when the photographic recording material is not always avoidable in an aldehyde-containing atmosphere. This situation can occur, for example, if photographic recording materials are stored in furniture, for their manufacture composite wood (e.g. plywood) or chipboard, which is used with a formaldehyde-releasing adhesive, e.g. a melamine-formaldehyde resin or a phenol-formaldehyde resin , have been glued.
  • a formaldehyde-releasing adhesive e.g. a melamine-formaldehyde resin or a phenol-formaldehyde resin
  • the formaldehyde from the gluing can cause more or less severe damage to the photographic layers, which in any case affects the quality of the photographic images produced with this material.
  • the loss of quality caused by the action of formaldehyde is particularly clear, since not only is an insufficient maximum color density obtained, but also the ⁇ balance of the three emulsion layers producing the color image is disturbed, which usually results in an intolerable color cast .
  • aldehydes in particular formaldehyde.
  • aldehyde scavengers are also possible.
  • DE-A-1 772 816 to add photographic layers, for example N, N'-ethylene urea, 2,3-dihydroxynaphthalene or dimedone, in order to fix formaldehyde.
  • DE-A-23 32 426 describes a photographic recording material which contains an acyclic urea as an aldehyde remover in addition to a vinylsulfonyl hardener in one of its colloid layers.
  • US-A-3 652 278 describes a method for reducing fog in photographic recording materials to be stored in an atmosphere containing formaldehyde. A compound from the group N, N'-ethylene urea, 2,3-dihydroxynaphthalene and 1,1-dimethyl-3,5-diketocyclohexane is then incorporated into the silver halide emulsion.
  • US-A-2,309,492 It is further known from US-A-2,309,492 to process photographic recording materials which contain an aldehyde hardener in the presence of an organic compound which is able to react with the aldehyde. These compounds include hydroxylamines, hydrazines, hydrazo compounds, semicarbazides, naphthalenediamines and dimethyldihydroresorcinol.
  • US-A-3 168 400 also relates to a method for stabilizing photographic images, which consists in curing the binder of the photographic material after exposure but before development with an aldehyde and then treating the unused aldehyde by treatment with the aqueous solution To remove amine compound.
  • Suitable amines are, for example, hydroxylamine, semicarbazide, hydrazine, biuret, aminoguanidine.
  • Photographic materials containing aldehyde are treated according to DE-A-22 27 144 in baths, the hydroxylamines and or contains a water-soluble salt of hydroxylamine and an aromatic polyhydroxyl compound with two hydroxyl groups in the ortho position, for example an o-dihydroxy compound from the benzene series.
  • the damaging influence of formaldehyde on the photographic layers is reduced by oxidation of the formaldehyde (DE-A-32 27 962).
  • DE-A-24 07 347 describes a photographic material which contains in a top layer a reaction product of gelatin with a monofunctional compound which is able to react with amino, imino, carboxyl and / or hydroxyl groups contained in the gelatin .
  • a reaction product of gelatin with a monofunctional compound which is able to react with amino, imino, carboxyl and / or hydroxyl groups contained in the gelatin .
  • the present invention has for its object to provide a photographic recording material with an improved stability against the action of formaldehyde.
  • the invention relates to a process for the production of a photographic recording material having at least one light-sensitive silver halide emulsion layer and at least one layer which contains a hardened proteinaceous binder which has free primary amino groups in the uncured state, characterized in that the proteinaceous binder at least one layer has a curing agent and a low molecular weight monofunctional compound which is capable of reacting with the free primary amino groups of the proteinaceous binder under casting and / or storage conditions.
  • the photographic recording material produced by the process according to the invention thus contains one or more binder layers with a proteinaceous binder, preferably gelatin, which has been hardened with a conventional hardening agent, the hardening agent being selected and dimensioned such that a desired maximum final hardening is achieved, in which the layers are sufficiently resistant to damage during processing and, on the other hand, the processability is still guaranteed.
  • a proteinaceous binder preferably gelatin
  • the hardening agent being selected and dimensioned such that a desired maximum final hardening is achieved, in which the layers are sufficiently resistant to damage during processing and, on the other hand, the processability is still guaranteed.
  • the curing agents used generally have two or more reactive groups which can react with free amino groups of the proteinaceous binder or, in the case of so-called carboxyl group-activating curing agents, at least one reactive group which can react with free carboxyl groups of the proteinaceous binder with activation of the latter, where a hardened binder matrix is formed by intermolecular linking (crosslinking) of different molecular strands of the proteinaceous binder. It has been observed that such a binder matrix, which has been hardened in a conventional manner until an optimal hardening state has been achieved, undergoes a change when formaldehyde is allowed to act on it.
  • a further hardening is apparently effected in this case, at the same time the through-developability is impaired, which manifests itself, for example, in less blackening in black-and-white materials and in color materials in a lower developable color density.
  • This effect does not occur or only to a lesser extent if the proteinaceous binder according to the present invention is reacted not only in the usual manner with a customary hardening agent, but simultaneously or subsequently with a low-molecular monofunctional compound which exhibits a reactive group which is associated with primary Amino groups of the proteinaceous binder can react, namely under Conditions in which the usual hardening is carried out, ie under casting and / or storage conditions.
  • the activated atom or the activated group X is preferably bonded to a carbon atom of an organic radical, which may be an aliphatic or araliphatic radical or a carbocyclic or heterocyclic aromatic radical.
  • an organic radical which may be an aliphatic or araliphatic radical or a carbocyclic or heterocyclic aromatic radical.
  • activated atoms X are in particular halogen atoms such as F, Cl, Br, J.
  • activated groups X are in particular -OSO2-M, -CN, -N3, -OCO-CH3, -SO2-M, where M is alkyl, aralkyl, aryl or -O-metal.
  • An activated group can, for example, also be an atom or a group which is bound intramolecularly via a further bond to another atom, preferably another C atom of the radical R, so that a cyclic structure results.
  • the displacement of the activated group from the first C atom takes place with the opening of the ring.
  • Examples of such compounds of the formula I with cyclic structures are compounds with an epoxy or ethyleneimine group.
  • the activating effect in this case presumably comes from the ring tension of the three-membered rings present.
  • the activating effect on the activated atom or the activated group X can also come about through the influence of neighboring polar groups.
  • An activated vinyl group represented by Y is especially a vinyl group attached to a polar group such as a sulfonyl, carbonyl, nitrile or phosphonate group is bound.
  • a polar group such as a sulfonyl, carbonyl, nitrile or phosphonate group is bound.
  • Such an activated vinyl group is capable of attaching primary amino groups.
  • such an activated vinyl group is bound to any organic radical via the activating polar group.
  • the amino group blockers used according to the invention are low molecular weight compounds with a molecular weight of less than 400 and preferably less than 200.
  • amino group blockers according to the invention are their monofunctionality. In the context of the present invention, this means that these compounds are able to react with primary amino groups of the proteinaceous binder under conditions to which photographic recording materials are usually exposed during production and, if appropriate, storage, without at the same time contributing significantly to curing.
  • the amino group blockers according to the invention therefore preferably contain only one functional group of the type shown in the formulas I and II. Compounds with more than one such functional group are also regarded according to the invention as "monofunctional" if they are reacted under conditions in which essentially only one of the functional groups present can react with an amino group of the binder, while the other no longer finds a reaction partner.
  • Such conditions exist, for example, when the amino group blockers according to the invention are used together with curing agents which react much more quickly, or when they only come into effect when curing has essentially been completed and the binder matrix has reached the desired final hardness.
  • amino group blockers (AB) examples are listed below:
  • the amino group blocking agents according to the invention are used alone or in a mixture of two or more in each case in combination with known hardeners.
  • specific examples of hardeners which can be used in combination with the amino group blocking agents according to the invention include aldehyde compounds such as formaldehyde, glutaraldehyde, ketone compounds such as diacetyl, cyclopentanedione, compounds with reactive halogen atoms such as bis- (2-chloroethylurea), 2-hydroxy-4 , 6-dichloro-1,3,5-triazine and similar compounds, for example described in US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207, Compounds with reactive olefins such as divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and like compounds described in US-A-3,635,71
  • inorganic hardeners such as chrome alum and zirconium sulfate can also be used can be used in combination.
  • inorganic hardeners such as chrome alum and zirconium sulfate can also be used can be used in combination.
  • those in the form of the corresponding precursors for example alkali metal bisulfite-aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic nitroalcohols, mesyloxyethylsulfonyl compounds, chloroethylsulfonyl compounds, chloroethylsulfonyl compounds, can also be used in combination.
  • hardeners are mostly compounds which are able to activate the carboxyl groups present in the proteinaceous binder so that the latter can react with the amino groups present in the proteinaceous binder.
  • Such hardeners are represented, for example, by the formulas III to VIII.
  • R1 and R2 (which may be the same or different) each represent alkyl having 1 to 8 carbon atoms (e.g. methyl, ethyl), aryl having up to 15 carbon atoms (e.g. phenyl, naphthyl) or aralkyl having up to 9 carbon atoms (e.g. benzyl, phenethyl) or they can be combined together to form a cyclic amino group (eg a pyrrolidine, piperazine, morpholine ring; R3 means hydrogen, halogen, carbamoyl, sulfo, ureido, alkoxy or alkyl.
  • R3 means hydrogen, halogen, carbamoyl, sulfo, ureido, alkoxy or alkyl.
  • the alkyl or Alkoxy groups can be further substituted, for example with a halogen atom, a carbamoyl group, a sulfo group or an ureido group.
  • X ⁇ represents an anion, but can be omitted if R3 contains a sulfo group in anionic form, so that an intramolecular salt is formed.
  • Suitable examples of an anion represented by X ⁇ include halide ions, C104 ⁇ , BF4 ⁇ , PF6 ⁇ , in the hardeners of formula IV R1, R2, R3 and X ⁇ have the same meaning as given for formula III.
  • R1 and R2 have the same meanings as defined for R1 and R2 in formula III, and R3 means alkyl with 1 to 10 carbon atoms (e.g. methyl, ethyl, butyl), aryl with up to 15 carbon atoms (e.g. phenyl, naphthyl) or aralkyl with up to 9 carbon atoms (e.g. benzyl, phenethyl).
  • X ⁇ has the same meaning as in Formula III.
  • Hardeners which can be used according to the invention are described in particular in DE-A-22 25 230, DE-A-23 17 677 and in German patent application P 35 23 360.5.
  • suitable hardeners are listed below:
  • Gelatin is preferably used as the proteinaceous binder, optionally mixed with other polymeric additives of natural or synthetic origin.
  • additives can be, for example, albumin, casein, cellulose derivatives, sugar derivatives, sodium alginate, starch derivatives, polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylic acid, polyacrylamides and others.
  • An important aspect in the selection and composition of the binder or binder mixture is that a sufficient amount of primary or in any case reactive amino groups is present in the uncured state in order to ensure adequate curing.
  • the swelling factor QF is a suitable measure for characterizing the hardening state. This means the ratio of the layer thicknesses in the swollen to the unswollen state.
  • a swelling factor in the Range from 1.5 to 3.5, preferably from 1.8 to 2.9. The swelling factor should not subsequently change significantly during storage, especially under the influence of formaldehyde.
  • the curing agent Since the swelling factor is essentially determined by the type and amount of the curing agent used in accordance with the invention, apart from an undesirable action by formaldehyde, the curing agent must be used under consideration of the other additives, in particular the amino group blocker according to the invention, under conditions such that the desired curing action is actually achieved. In general, however, in particular if the amino group blocker to be used and the hardening agent to be used are approximately equally reactive, these two additives can be added simultaneously or in succession. The dosage of these two compounds is to be selected so that the desired final hardening state is achieved in any case by the added hardener, whereby no substantial change in this final hardening state is to be achieved by the additional action of the amino group blocker.
  • the easiest way to achieve this is to add the hardening agent in the amount required for the hardening and to add the amino group blocker only when the desired hardening state has already been substantially achieved.
  • the amount of the amino group blocker to be used is not critical in this connection, provided that it is used at least in such an amount to largely block the amino groups of the proteinaceous binder that are not used in the curing reaction, and thus one to withdraw undesired further reaction with formaldehyde. Of course, no further hardening should be brought about by the reaction with the amino group blocker. Since the amino group blockers according to the invention, if they contain only one reactive group, cannot in fact cause curing, it is clear that the objects of the invention are achieved with this embodiment.
  • the hardened binder matrix produced by hardening with the hardening agent creates conditions in which, according to the invention, even amino group blockers which have two or more groups which are potentially reactive with amino groups and which are therefore potential hardeners cannot make a significant contribution to hardening, because at most one of the reactive ones Groups reacted with a free amino group, while other reactive groups present found in suitable spatial proximity in the hardened binder matrix no further free amino groups. Therefore, such amino group blockers with several reactive groups, at least in this embodiment, are also de facto to be referred to as "monofunctional".
  • the dosage of the amino group blocker must be carried out fairly precisely, because in this reaction there should in any case be just enough amino groups remaining that the desired curing state can still be achieved in the subsequent curing. If the amino group blocker is used in too large an amount, subsequent hardening can no longer take place. On the other hand, if this amount is too small, amino groups remain even after curing the undesirable reaction with formaldehyde is available, so that in this case the objectives of the invention are only incompletely achieved.
  • suitable amounts of hardener and amino group blocker can be carried out by routine series tests and presents no problem for the person skilled in the art. The same also applies in the case that hardener and amino group blocker are used simultaneously, in which case, in particular, a different reactivity of the two additives must be taken into account and taken into account.
  • Hardener and amino group blocker can be added to the casting solution at the same time, but also one after the other. They can be added to one, several or even all layers of the photographic recording material. They can be added to one or more layers with which the photographic recording material is overlaid. They can also be added separately, for example by adding the hardener to one, several or all of the essential layers of the photographic recording material and applying the amino group blocker by overlaying the photographic material thus prepared with a layer which contains the amino group blocker in sufficient quantity is, or as Example 1 teaches, treated with a solution containing the amino group blocker. The reverse way of working is also possible.
  • the light-sensitive silver halide emulsions used in the light-sensitive layers can contain chloride, bromide and iodide or mixtures thereof as the halide.
  • the halide content of at least one layer can consist of 0 to 12 mol% of iodide, 0 to 50 mol% of chloride and 50 to 100 mol% of bromide.
  • the crystals are predominantly compact, e.g. are cubic or octahedral or have transitional forms. They can be characterized in that they essentially have a thickness of more than 0.2 ⁇ m.
  • the average ratio of diameter to thickness is preferably less than 8: 1, it being true that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. In other embodiments, however, all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.
  • the emulsions can be heterodisperse or else monodisperse emulsions, which preferably have an average grain size of 0.3 ⁇ m to 1.2 ⁇ m.
  • the silver halide grains can also have a layered grain structure.
  • the emulsions can contain the usual casting aids and plasticizers. Reference is made to Research Disclosure 17643 December 1978, in particular Chapter, XI and XII.
  • the emulsions can be chemically and or spectrally sensitized in the usual way.
  • Suitable chemical sensitizers, spectral sensitizing dyes and stabilizers are described, for example, in Research Disclosure 17643; Reference is made in particular to chapters III, IV and VI.
  • the invention can be applied to any type of photographic recording material which contains proteinaceous binders as layer binders, it is particularly advantageous when used on color photographic recording materials, in particular those which contain color couplers and which are processed by the chromogenic development process.
  • Color photographic recording materials usually contain at least one silver halide emulsion layer for recording light from each of the three spectral ranges red, green and blue.
  • the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes.
  • Blue-sensitive silver halide emulsion layers do not necessarily have to contain a spectral sensitizer, since in many cases the intrinsic sensitivity of the silver halide is sufficient for the recording of blue light.
  • Each of the light-sensitive layers mentioned can consist of a single layer or, in a known manner, for example in the case of the so-called double-layer arrangement, can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • Red-sensitive silver halide emulsion layers are usually the support arranged closer than green-sensitive silver halide emulsion layers and these, in turn, closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • a layer which is not sensitive to light is generally arranged between layers of different spectral sensitivity and can contain means for preventing the incorrect diffusion of developer oxidation products.
  • silver halide emulsion layers of the same spectral sensitivity can be immediately adjacent to one another or arranged in such a way that a light-sensitive layer with a different spectral sensitivity is located between them (DE-A-1 958 709, DE-A-2 530 645, DE-A -2 622 922).
  • Color photographic recording materials for producing multicolored images usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, coloring compounds, here in particular color couplers, for producing the different partial color images cyan, purple and yellow,
  • Color coupler is in such a spatial relationship to the silver halide emulsion layer that an interaction between them is possible which creates an image-like correspondence between the silver image formed during development and that produced from the color coupler Color picture allows. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in a possibly non-light-sensitive binder layer adjacent to it.
  • Spectral assignment is understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler are in a specific relationship to one another, with each of the spectral sensitivities (red, green, blue) having a different color partial color image ( in general, for example, the colors cyan, purple or yellow are assigned in this order).
  • Each of the differently spectrally sensitized silver halide emulsion layers can be assigned one or more color couplers. If there are several silver halide emulsion layers of the same spectral sensitivity, each of them can contain a color coupler, whereby these color couplers need not necessarily be identical. They should only result in at least approximately the same color during color development, normally a color that is complementary to the color of the light, for which the silver halide emulsion layers in question are predominantly sensitive,
  • Red-sensitive silver halide emulsion layers are thus at least one in preferred embodiments assigned to the non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
  • Green-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone, indazolone or pyrazoloazole type are usually used, blue-sensitive silver halide emulsion layers are finally assigned to at least one non-diffusing color coupler for generating the yellow partial color image a color coupler with an open chain ketomethylene grouping.
  • Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publications “Color Coupler” by W. PELZ in “Messages from the research laboratories of Agfa, Leverkusen / Kunststoff", Volume III, page 111 (1961) and by K. VENKATARAMAN in “The Chemistry of Synthetic Dyes", Vol , 4, 341 to 387, Academic Press (1971).
  • the color couplers can be both conventional 4-equivalent couplers and 2-equivalent couplers in which a smaller amount of silver halide is required to produce the color.
  • 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling.
  • the 2-equivalent couplers include both those that are practically colorless and those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced.
  • the latter couplers can also be present in the light-sensitive silver halide emulsion layers and serve there as mask couplers to compensate for the undesired secondary densities of the image dyes.
  • the known white couplers are also to be counted among the 2-equivalent couplers, but they do not give any dye on reaction with color developer oxidation products.
  • the 2-equivalent couplers also include those couplers which contain a detachable residue in the coupling point, which is released when reacting with color developer oxidation products and which exhibits a certain desired photographic activity, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.
  • the cleavable residue can also be a ballast residue, so that in the reaction with color developer oxidation products coupling products, for example dyes, can be obtained which are diffusible or at least have a weak or restricted mobility.
  • Weak or restricted mobility means mobility that is dimensioned such that the contours of the discrete dye spots formed in the chromogenic development run and are smeared into one another.
  • This degree of mobility is on the one hand to be distinguished from the usual case of complete immobility in photographic layers, that of conventional photographic recording materials for the color couplers or the dyes produced therefrom in order to achieve the highest possible sharpness, and on the other hand the case of the complete mobility of the dyes, which is sought for example in color diffusion processes.
  • the latter dyes usually have at least one group that makes them soluble in the alkaline medium.
  • the extent of the weak mobility sought according to the invention can be controlled by varying substituents in order to influence, for example, the solubility in the organic medium of the oil former or the affinity for the binder matrix in a targeted manner.
  • High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A- 33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
  • the high molecular weight color couplers are generally produced by polymerizing ethylenically unsaturated monomeric color couplers .
  • Examples include: 1H-imidazo [1,2-b] pyrazoles (eg pyrazolobenzimidazoles), 1H-pyrazolo [1,5-b] pyrazole, 1H-pyrazolo [5,1-c] 1,2,4-triazoles 1H-pyrazolo [1,5-b] 1,2,4-triazoles and 1H-pyrazolo [1,5-d] tetrazoles, Particularly useful special pyrazoloazoles PA are given in the following overview:
  • the photographic recording material of the present invention can contain further conventional additives, such as, for example, antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
  • additives such as, for example, antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
  • UV-absorbing compounds in one or more of the layers contained in the recording material, preferably in one of the upper layers use. Suitable UV absorbers are described, for example, in US Pat. No. 3,253,921, DE-C-2,036,719 and EP-A-0 057 160,
  • the recording material according to the invention which contains at least one silver halide emulsion layer and at least one color coupler of the formula I assigned to it, is developed with a color developer compound.
  • All developer compounds which have the ability in the form of their oxidation product to react with color couplers to form azomethine or indoquinone dyes can be used as the color developer compound.
  • Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-eth
  • the recording materials A, B, C and D thus produced were further treated in five different test series after different pretreatment as follows. They were stored for 1 week at room temperature, then for 1 week in an atmosphere with 4 ppm formaldehyde at 70% relative humidity, then exposed behind a gray wedge and processed according to a negative development process described in "The British Journal of Photography, 1974, pages 597 and 598.
  • the recording materials E to J were stored at room temperature for 1 week.
  • the swelling factor QF was then determined.
  • a sample of each material was stored in a formaldehyde-free atmosphere. Additional samples were stored for 3, 7, 14 or 21 days in an atmosphere with 4 ppm formaldehyde at 70% relative humidity. Then all samples were selectively exposed to green light and processed as in Example 1.

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Claims (6)

  1. Procédé pour la préparation d'un matériau d'enregistrement photographique contenant au moins une couche photosensible d'émulsion à l'halogénure d'argent et au moins une couche gui contient un liant protéinique durci qui, à l'état non durci, présente des groupes amino primaires libres, caractérisé en ce qu'on laisse agir, sur le liant protéinique comprenant au moins une couche, un agent de durcissement et un composé monofonctionnel à bas poids moléculaire qui est susceptible de réagir dans des conditions de coulée et/ou d'entreposage, avec les groupes amino primaires libres du liant protéinique.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on laisse agir, sur le liant protéinique comprenant au moins une couche, d'abord un agent de durcissement et ensuite le composé monofonctionnel à bas poids moléculaire qui est susceptible de réagir avec les groupes amino primaires libres dans des conditions de coulée et/ou d'entreposage.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le composé monofonctionnel à bas poids moléculaire qui est susceptible de réagir avec les groupes amino primaires libres dans des conditions de coulée et/ou d'entreposage, répond à une des formules I et Il ci-après :



            X - R   I




            Y -R'   II



    dans laquelle
    X   représente un atome activé ou un groupe activé qui est lié à un atome de carbone du radical R et qui peut en être déplacé par un atome d'azote d'un groupe amino primaire;
    R   représente un radical organique contenant au moins un groupe par lequel l'atome ou le groupe X est activé;
    Y   représente un groupe activé auquel peut se fixer, par addition, un groupe amino primaire dans une réaction d'addition 1,2- ou 1,4-;
    R'   représente un radical organique par lequel éventuellement le groupe Y peut être activé.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que, comme agent de durcissement, on utilise un agent de durcissement activant les groupes carboxyle.
  5. Procédé selon la revendication 4, caractérisé en ce que l'agent de durcissement activant les groupes carboxyle répond à la formule ci-après :
    Figure imgb0034
     dans laquelle
    R¹ et R²   (qui peuvent être identiques ou différents) représentent un groupe alkyle contenant de 1 à 8 atomes de carbone ou un groupe aralkyle contenant jusqu'à 9 atomes de carbone ou bien R¹ et R² représentent conjointement avec l'atome N un groupe amino cyclique;
    R³   représente un atome d'hydrogène, un atome d'halogène, un groupe carbamoyle, un groupe sulfo, un groupe uréido, un groupe alcoxy ou un groupe alkyle.
    X⊖   représente un anion, mais qui peut ne pas exister lorsque R³ contient un groupe sulfo sous forme anionique.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le matériau d'enregistrement photographique contient un copulant pyrazoloazole répondant à la formule ci-après :
    Figure imgb0035
     dans laquelle
    R¹   représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcoxy, un groupe amino, un groupe acylamino, un groupe anilino;
    X   représente un atome d'hydrogène ou un groupe apte à se séparer par couplage chromogène;
    Za, Zb et Zc   représentent chacun un groupe méthine éventuellement substitué, =N- ou NH-.
EP87103219A 1986-03-18 1987-03-06 Procéde de préparation d'un matériau d'enregistrement photographique Expired - Lifetime EP0237887B1 (fr)

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DE3608998 1986-03-18
DE19863608998 DE3608998A1 (de) 1986-03-18 1986-03-18 Fotografisches aufzeichnungsmaterial

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EP0237887A2 EP0237887A2 (fr) 1987-09-23
EP0237887A3 EP0237887A3 (en) 1990-02-07
EP0237887B1 true EP0237887B1 (fr) 1993-02-03

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JPH07119993B2 (ja) * 1987-01-19 1995-12-20 コニカ株式会社 ハロゲン化銀写真感光材料
JPH07119992B2 (ja) * 1987-01-19 1995-12-20 コニカ株式会社 ハロゲン化銀写真感光材料
DE3740930A1 (de) * 1987-12-03 1989-06-15 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial mit einem phenolischen blaugruenkuppler
US5858460A (en) * 1991-07-01 1999-01-12 The United States Of America As Represented By The Secretary Of The Navy Metal matrices reinforced with silver coated boron carbide particles
EP0576912B1 (fr) * 1992-06-29 1997-10-22 Sterling Diagnostic Imaging, Inc. Modification in situ des groupes de carboxyle de gélatine
US5411856A (en) * 1994-01-10 1995-05-02 Eastman Kodak Company Carbamyl-substituted bis(vinylsulfonyl) methane hardeners

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Publication number Priority date Publication date Assignee Title
US3132945A (en) * 1960-07-13 1964-05-12 Polaroid Corp Silver halide emulsions containing vinyl sulfone-gelatin derivatives
JPS578455B2 (fr) * 1973-02-15 1982-02-16
US3840370A (en) * 1973-05-07 1974-10-08 Eastman Kodak Co Controlling after-hardening in hardenable hydrophilic colloids
JPS5639668B2 (fr) * 1974-02-13 1981-09-14
DE2625026A1 (de) * 1976-06-03 1977-12-22 Agfa Gevaert Ag Verfahren zur haertung photographischer gelatinehaltiger schichten
DE2924035A1 (de) * 1979-06-13 1981-01-08 Agfa Gevaert Ag Verfahren zur kettenverlaengerung von gelatine durch partielle haertung
DE3224983A1 (de) * 1982-07-03 1984-01-05 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur haertung photographischer gelatine mit sulfonyl-ethylsulfatgruppenhaltigen vinylsulfonen
JPS60170841A (ja) * 1984-02-16 1985-09-04 Fuji Photo Film Co Ltd ゼラチン硬化方法
JPS60258545A (ja) * 1984-05-10 1985-12-20 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPS61123834A (ja) * 1984-10-23 1986-06-11 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料

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DE3783926D1 (de) 1993-03-18
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EP0237887A2 (fr) 1987-09-23
EP0237887A3 (en) 1990-02-07
US4939079A (en) 1990-07-03

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