Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—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 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 layer support and light-sensitive gelatin-containing silver halide emulsion layers applied thereon and, if appropriate, non-light-sensitive auxiliary layers likewise containing 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 come into the color as hardening agents, which are able to crosslink the gelatin via the carboxyl groups and / or the amino groups.
• 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 "-Trisacryloyl-perhydro-s-triazine called.
• 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 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 V-compensation of the three emulsion layers producing the color image is sensitively 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).
• 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 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 hardened proteinaceous binder has amino groups of the formula -NH-R , wherein R is the residue of a low molecular weight monofunctional compound which has been reacted with the free primary amino groups of the proteinaceous binder under casting and / or storage conditions.
• the photographic recording material 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 ensured.
• 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 ensured.
• a further hardening is apparently effected in this case, at the same time the through-developability is impaired, which manifests itself, for example, in the case of black-and-white materials in a lower blackening or in the case of 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 -SO 2 -M, where M is alkyl, aralkyl, aryl or -0-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 presumably comes about through 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 activated vinyl group is befä - higt attach 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.
• amino group blockers According to the invention, 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 the curing has essentially been completed and the binder matrix has reached the desired final hardness.
• Examples of amino group blockers (AB) according to the invention 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-diacryloylhexa hydro-1,3,5-triazine and similar compounds described in US-A-3,635,718,
• 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.
• R 1 and R 2 (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 with one another to form a cyclic amino group (for example a pyrrolidine, piperazine or morpholine ring; R 3 denotes hydrogen, halogen, carbamoyl, sulfo, ureido, alkoxy or alkyl.
• R 3 denotes hydrogen, halogen, carbamoyl, sulfo, ureido, alkoxy or alkyl.
• the alkyl radicals represented by R 3 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 R 3 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, C10 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ .
• R 1 , R 2 , R 3 and X have the same meaning as given for formula III.
• R 1 and R 2 have the same meanings as defined for R 1 and R 2 in formula III, and R 3 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.
• 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.
• Spatial assignment is understood to mean that the color coupler is in such a spatial relationship to the silver halide emulsion layer that an interaction between them is possible which produces an image-like correspondence between the silver image formed during development and that from the color coupler color image. 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).
• One or more color couplers can be assigned to each of the differently spectrally sensitized silver halide emulsion layers. If there are several silver halide emulsion layers of the same spectral sensitivity, each of them can contain a color coupler, which 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 ⁇ x-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 usually being used.
• blue-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for producing the yellow partial color image, usually 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. Example here on the publications “color - coupler” by W. FUR 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 either conventional 4-equivalent couplers or 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 inherent color that ver with the color coupling disappears 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.
• Such couplers are 2-equivalent couplers also to be those which contain a releasable group in the coupling position, the arbentwickleroxidations impn upon reaction with F is set in Feiheit, thereby mecanic.bestimmte desired photographic effect deployed, 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 must be distinguished on the one hand from the usual case of complete immobility in photographic layers, that of conventional photographic recording material alien for the color coupler or the dyes made from it is sought in order to achieve the highest possible sharpness, and on the other hand from the case of the complete mobility of the dyes, for example in the case of dyes. diffusion process is sought.
• 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 .
• 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 formula 1 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-ethyl
• 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 Phtography, 1974, pages 597 and 598.

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• 1986
  • 1986-03-18 DE DE19863608998 patent/DE3608998A1/de not_active Withdrawn
• 1987
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