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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/30—Hardeners
  • G03C1/306—Hardeners containing an oxirane ring

Definitions

• the invention relates to a photographic recording material in which the layers containing proteinaceous binders are hardened by heterocyclic epoxy compounds.
• the mechanical strength of uncured gelatin layers is not sufficient for the stresses that occur during practical processing. Swollen gelatin layers are extremely sensitive to mechanical injuries and thermal stress, since the melting point of gelatin (approx. 30 ° C) is very low.
• hardening agents are added to the emulsions, which react with the gelatin to form cross-connections between the individual peptide chains. The swellability and drying time are reduced, the melting temperature and wet strength are increased, so that swollen layers become more resistant to damage.
• 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 vinylsulfones, acrylamides, compounds with at least two easily cleavable, heterocyclic 3-membered rings such as ethylene oxide and ethyleneimine, 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,
• high molecular weight curing agents such as polyacrolein or its derivatives or copolymers, and alginic acid derivatives have become known, which are used specifically as layer-limited curing agents.
• hardening agents for photographic gelatin layers are compounds with two or more acrylic acid amido groups in the molecule, N, N ', N oder-trisacryloylhydrotriazine or methylenebisacrylamide.
• the hardening of the compounds is good after some time, but the compounds are sparingly soluble in water, which can lead to irregularities in the hardening within the layer.
• DE-B 1 808 685 and DE-A 2 348 194 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 enable their use in gelatin photographic layers, or they adversely affect the drying behavior of the layers. It has been found to be particularly disadvantageous that these compounds increase the viscosity of the casting solution in such a way that the casting is considerably disturbed.
• bis- and polyethylene oxide compounds of aliphatic ethers, esters and amines are known as crosslinking agents for photographic gelatin-containing materials. In many cases, they cannot be used for toxicity. It was therefore switched to less toxic compounds such as di- and triglycidyl ether from triazine or isocyanurate compounds or even from silicon compounds (DE-A 1 085 663).
• a disadvantage is the rapid breakdown of the crosslink bonds in alkaline baths at temperatures above 30 ° C., as are used in rapid photographic processing. It has also proven to be a disadvantage that the hardening effect decreases with the increasing distance between the epoxy groups in the molecule.
• the wet scratch resistance of a gelatin layer hardened with diglycidether is greater than that of the layer hardened with bis (epoxypropyl) ethylene glycol ether.
• the invention is based on the object of developing a photographic recording material in which the layers containing proteinaceous binders can be hardened by a hardening agent in such a way that faults do not occur during the casting process.
• viscosity increases caused by premature crosslinking of the proteinaceous binders have a disadvantageous effect.
• the photographic properties must not be negatively influenced, nor should difficulties arise when the materials are subsequently processed in photographic baths. There are properties like high layer melting point, low swellability and high wet scratch resistance of the photographic layers are sought.
• the invention relates to a photographic recording material with at least one layer containing a proteinaceous binder, characterized in that the proteinaceous binder with a compound of formula I, wherein R1 is hydrogen or methyl, preferably hydrogen, m is the number 0 or 1 and R2 for the case that is 0, the rest a monovalent, unsubstituted or substituted linear or branched aliphatic C1-C18-, preferably C1-C12-, a monovalent, unsubstituted or substituted cycloaliphatic C5-C6-, a monovalent, unsubstituted or substituted aliphatic-aromatic C7-C10- or a monovalent unsubstituted or substituted aromatic C6-C10 radical, and for the case that m is 1, a divalent unsubstituted or substituted, linear or branched aliphatic C2-C18-, preferably C2-C12-, a divalent unsubstituted or substituted cycl
• R2 Possible substituents on R2 are: C1-C4-alkoxy, CN, NO2, C1-C4-alkylmercapto, halogen, preferably fluorine, chlorine, bromine, and in the case of the cycloaliphatic and aromatic radicals additionally C1-C4-alkyl.
• the 1,2-polyepoxides of the formula (I) can be obtained by using the known triazolidine-3,5-diones of the formula (II) wherein m is 0 or 1, R3 for the case that m is 0, hydrogen or an optionally substituted, monovalent aliphatic C1-C18, cycloaliphatic C5-C6, aliphatic-aromatic C7-C10 or aromatic C6-C10 radical and for the case that m 1 is a divalent, optionally substituted aliphatic C2-C18, cycloaliphatic C5-C12, aliphatic-aromatic C7-C10 or aromatic C6-C10 radical, with excess epichlorohydrin or ⁇ -methylepichlorohydrin in the presence of a suitable catalyst, for example triethylamine, in a manner known per se at 20-200 ° C. to give the triazolidine-3,5-dione-polychlorohydrin and then with agents which release
• polyglycidyl compounds are prepared by e.g. in US-A-4,283,546 and US-A-4,467,099.
• the poly-glycidyl-triazolidine-3,5-diones obtained have epoxy values from 0.2 to 1.12, preferably from 0.6 to 1.12.
• the epoxy value is understood to mean the number of 1,2-epoxy groups contained in 100 g of substance. The determination is carried out by titration with hydrochloric acid, one mole of 1,2-epoxide groups being equivalent to one mole of hydrogen halide.
• the hardening agents used according to the invention can be added to the casting solution of a binder layer to be produced, for example a photographic layer, either for some time or immediately before casting, using suitable metering devices.
• the compounds can also be added to a coating solution which, after the actual binder layer has been produced, is applied to it as a hardening layer.
• the finished layer structure can also be drawn through a solution of the hardening agent and thereby receives the necessary amount of hardening agent.
• the crosslinkers of the invention can be introduced into the overall structure via the intermediate layers.
• the hardening agents according to the invention are generally used in an amount of 0.01 to 15% by weight and preferably 0.1 to 5% by weight, based on the dry weight of the protein, preferably the gelatin, in the coating solution.
• the timing of the addition to the coating solution is not critical; Silver halide emulsions will expediently add the hardener after chemical ripening. pH-controlling compounds such as bicarbonate or sodium acetate can be used together with the curing agents according to the invention.
• the curing agents according to the invention can be used individually or as a mixture of two or more compounds according to the invention, or together with other known curing agents.
• Suitable additional hardening agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds which are reactive Contain halogen as described in US-A-3,228,775, US-A-2,732,303, GB-A-974,723 and GB-A-1,167,207; Divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other compounds containing a reactive olefin linkage, such as in US-A-3,635,718, US-A-3,232,763
• Patent Nos. 3,321,313 and 3,543,292 Halogen carboxyaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.
• the curing agents of the invention can be used together with precursors of the compounds described above, such as with alkali metal bisulfite-aldehyde adducts, methylol derivatives of hydantoin and primary fatty nitro alcohols, etc.
• the amount of the curing agents of the present invention can be selected as needed, depending on the purpose and the effect.
• the protein of the hardened binder layer according to the present invention typically serves as a binder for reactive or non-reactive substances dispersed therein, e.g. Dyes or compounds that undergo a change, for example upon exposure or subsequent processing, and thereby develop a certain effectiveness.
• the binder layers hardened according to the invention can be present, for example, in the form of colored coatings.
• the hardened protein can also be used in photographic or photothermographic single or multilayer recording materials, e.g. as a binder for silver halide, color couplers and other photographically active substances.
• photographic layers are to be understood in general terms as layers which are used in the context of photographic recording materials, for example light-sensitive silver halide emulsion layers, protective layers, filter layers, antihalo layers, backing layers, image-receiving layers or very generally photographic auxiliary layers.
• light-sensitive gelatin-containing emulsion layers for the hardening of which the hardening agents according to the invention are excellently suitable, mention may be made, for example, of layers which contain light-sensitive substances, in particular silver halide, optionally in a spectrally sensitized form.
• layers are usually contained in photographic recording materials for a wide variety of photographic black-and-white or color processes, such as negative, positive, diffusion transfer or printing processes.
• the curing agents according to the invention have proven to be particularly advantageous for the curing of photographic layer dressings which are intended for carrying out color photographic processes, e.g. those which contain color couplers or other coloring compounds or those which are intended for treatment with solutions containing color couplers.
• the effect of the hardening agents according to the invention is not impaired by the usual photographic additives.
• the hardeners are also indifferent to photographically active substances, such as water-soluble or emulsified water-insoluble color components, stabilizers, sensitizers and the like. Furthermore, they have no adverse effect on the light-sensitive silver halide emulsion.
• the light-sensitive component in the light-sensitive silver halide 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.
• it can be compact crystals which are, for example, cubic or octahedral or which can have transitional forms. 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.
• the layers can also have 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 also contain organic silver salts, for example silver benzotriazolate or silver behenate.
• the emulsions can be chemically and or spectrally sensitized in the usual way; they can also be stabilized by suitable additives. 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 binder mainly used according to the invention is a protein-like binder, in particular gelatin.
• An essential feature of this binder is the presence of functional groups with which the vinylsulfonyl groups of the curing agent according to the invention can react, in particular amino groups.
• the proteinaceous binder can be partially e.g. be modified by partial acylation or be replaced by other natural or synthetic binders as long as sufficient reactivity with the curing agent according to the invention is maintained. Casting aids and plasticizers can be used. Reference is made to Research Disclosure 17 643, in particular Chapters IX, XI and XII.
• the binder layer can contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a so-called spacer. Such particles can consist of an organic polymer.
• photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a so-called spacer.
• Such particles can consist of an organic polymer.
• wetting agents - preferably anionic wetting agents - are added to the layers.
• R-CH2-O-SO3 ⁇ Me ⁇ R C10-C17 Succinic acid ester sulfonates Alkylmethyltaurine, mono- and dialkylnaphthalenesulfonates and perfluoroalkylsulfonates are used.
• Me ⁇ are, for example, Li ⁇ , Na ⁇ , K ⁇ NH4 ⁇ and N (C2H5) 4 ⁇ .
• 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, also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
• Red-sensitive silver halide emulsion layers are usually closer to the support, green-sensitive silver halide emulsion layers are arranged closer to them, and these are 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 the production of multicolored images usually contain, in spatial and spectral association with the silver halide emulsion layers of different spectral sensitivity, coloring compounds, e.g. Color coupler, for generating the different partial color images cyan, purple and yellow.
• coloring compounds e.g. Color coupler
• Spatial assignment is understood to mean that the color coupler is in such a spatial relationship with the silver halide emulsion layer that an interaction between them is possible which allows an image-wise match between the silver image formed during development and the color image generated from the color coupler. 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 of the relevant partial color image (in general, for example, the colors cyan, purple or yellow 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 therefore assigned at least one 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 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.
• 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 when reacted with color developer oxidation products.
• the 2-equivalent couplers are also those couplers which contain a detachable residue in the coupling point which is released when reacting with color developer oxidation products, and either directly or after one or more groups have been split off from the split-off residue (for example DE-A-27 03 145, DE A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic Efficacy unfolds, for example as a development inhibitor or accelerator.
• 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 to be distinguished on the one hand from the usual case of complete immobility in photographic layers, which is sought in the 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 from the case of 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 Variation of substituents in order to influence, for example, the solubility in the organic medium of the oil former or the affinity for the binder matrix.
• 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 . However, they can also be obtained by polyaddition or polycondensation.
• the binder layers can contain filter and antihalation dyes, for example oxonol dyes as described in US Pat. Nos. 2,274,782, 2,611,696, FR-1,290,430, GB-A 1 177 429, DE-A-1 572 256, DE-A-22 59 746, DE-A-23 21 470, US-A-3 984 246, styryl dyes as described in US-A-2 036 546, DE-B-1 014 430, DE-B -1-028 425, DE-B-1 112 801, DE-B-1 104 335, azo dyes as described in DE-B-1 103 135, DE-B-1 182 067, GB-A-1 122 298, DE-A-1 547 646, triphenylmethane dyes as described in DE-B-1 008 114, anthraquinone dyes as described in US-A-2 865 752 or merocyanines as described in GB-A-1 030 392 or
• the binder layers can contain UV absorbers, optionally also in high molecular weight.
• UV absorbers optionally also in high molecular weight.
• the binder layers can contain dye stabilizers, as described in DE-A-35 01 722, EP-A-0 011 051, EP-A-0 026 742, EP-A-0 069 070, EP-A-0 098 241, EP -A-0 114 028, EP-A-0 114 029, and Research Disclosure 17 643, Chapter VII, in particular Section J.
• the binder layers can contain optical brighteners or white toners. Reference is made, for example, to Research Disclosure 17 643, Chapter V.
• the binder layers can contain so-called scavenger compounds, ie compounds that react with developer oxidation products and are able to prevent them from diffusing into neighboring layers.
• scavenger compounds ie compounds that react with developer oxidation products and are able to prevent them from diffusing into neighboring layers.
• the compounds to be introduced can be added by first preparing a solution or a disperse from the compounds in question and then adding them to the casting solution.
• the solvent or dispersant depends on the respective need.
• Hydrophobic compounds can be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described, for example, in US-A-2 322 027, DE-A-1 722 192 and EP-A-0 043 037.
• the compounds can also be introduced into the casting solution in the form of loaded latices.
• the binder layers can furthermore contain agents which are able to react with aldehydes, in particular with formaldehyde, so-called aldehyde removers, or compounds which are able to protect other embedded compounds, in particular other color couplers, against the harmful influence of aldehydes.
• aldehyde removers include, for example, N, N'-ethylene urea, 2,3-dihydroxynaphthalene or dimedone. Reference is made, for example, to DE-A-1 772 816.
• the recording material according to the invention is developed with a color developer compound.
• All developer compounds that can be used as color developer compounds Able to react in the form of their oxidation product with color couplers to form azomethine or indoquinone dyes.
• 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.
• Other useful color developers are described for example in J. Amer. Chem. Soc. 73 , 3106 (1951) and in G. Haist, Modern Photographie Processing, 1979, John Wiley and Sons, New York, page 545 ff.
• the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
• the usual compounds can be used as bleaching agents, e.g. Fe3+ salts and Fe3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc.
• Particularly preferred are iron III complexes of aminopolycarboxylic acids, especially e.g. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulphates are also suitable as bleaching agents.
• the mixture was stirred well and poured onto a cellulose triacetate pad with a conventional casting machine and dried.
• the material was each one day at 23 ° C and 3 days under tropical conditions 36 ° C / 90% rel. Moisture stored and then tested for crosslinking 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.
• 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 base (streak formation) is referred to as the layer melting point or melting point. According to this measuring method, uncured protein layers never show an increase in melting point.
• the layer melting point is 30 to 35 ° C under these conditions.
• the swelling is measured gravimetrically after treatment of a test strip in distilled water at 22 ° C. for 10 minutes. It is denoted 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.
• the compounds H 1, H 2 and H 4 according to the invention produce boil-resistant layers (layer melting points above 100 ° C.) and high wet scratch resistance even after storage for 1.5 days, in contrast to the comparison compounds VV1 and VV2, which show good hardening only after 3 days of tropical storage.
• the compounds according to the invention act faster and are therefore significantly different from the comparison compounds.
• the pouring solutions can be left to stand for one hour without increasing the viscosity, a sign of the desired low reaction of the compounds according to the invention with gelatin in solution.
• the layers showed no serious differences compared to the uncured layer after development and fixation. Sensitivity, fog values and the ⁇ values did not change. The hardeners remained inert towards the halosilver emulsion even after the layers had been stored for a long time.
• the layer structure was at least 34% rel. 36 hours at 75 ° C. Humidity and 7 days at 36 ° C and 80% rel. Humidity stored.
• the photographic properties differ only slightly from the samples cast with conventional hardeners.
• crosslinking values apply to the layers after processing in standard processing baths that are 38 ° C warm.
• the hardening system is inert towards the emulsions and the color couplers.
• the hardening effect is also excellent in gelatin-containing photographic black and white materials. 5 g of the compounds H 1, H 3 and H 6 were used per 100 g of gelatin. The casting solutions contained 35 g of silver halide. The hardening properties were tested after storage of the material under 4 different climatic conditions. climate condition 1: 23 ° C, moisture exclusion 2 days climate condition 2: 23 ° C, moisture exclusion 7 days climate condition 3: 57 ° C, 34% rel. Humidity 36 hours climate condition 4: 36 ° C, 90% rel. Humidity 7 days.
• Samples of a photographic paper emulsion containing 80 g of gelatin and 35 g of silver halide per liter and each 3% by weight of a crosslinking agent according to the invention were poured onto polyethylene-backed paper substrates which had been provided with an adhesive layer.
• the usual pouring aids such as wetting agents, stabilizers and optical sensitizers had been added to the emulsion samples beforehand.
• the layer melting points were determined directly after drying.
• the layer melting points were determined after passing through a 22 ° C photographic developer bath for black and white materials.
• the developer solution had the following composition: 6 g metol 3 g hydroquinone 30 g sodium sulfite 25 g anhydrous soda 2 g potassium bromide Water to 1 1.
• the example shows that the curing agents according to the invention crosslink relatively quickly and the crosslinking in the alkaline developer solution is not reduced again but is increased.
• Harder Melting point after drying Melting point after developer bath 1 1/2 3 min.
• H 1 100 ° C 100 ° C 100 ° C H 3
• 100 ° C 100 ° C 100 ° C H 4 100 ° C 100 ° C 100 ° C H 5 50 ° C 100 ° C 100 ° C
• Samples of a photographic paper emulsion containing 80 g of gelatin and 35 g of silver halide per liter and each 5 g of crosslinker per 100 g of gelatin were poured onto polyethylene-backed paper supports provided with an adhesive layer.
• the usual Pouring aids such as wetting agents, stabilizers and optical sensitizers were previously added to the emulsion samples.
• the layer melting points and the wet scratch resistance were determined after passing through a photographic developer bath at 20 ° C., 38 ° C. and 50 ° C.
• the developer solution corresponded to that of Example 4 Table 4 Harder Developer temperature 20 ° C 38 ° C 50 ° C Layer melting point Swelling factor Wet scratch resistance (N) Layer melting point Swelling factor Wet scratch resistance (N) Layer melting point Swelling factor Wet scratch resistance (N) H 1 100 ° C 2.1 > 9.81 100 ° C 2.5 > 9.81 100 ° C 2.5 > 9.81 H 4 100 ° C 2.2 > 9.81 100 ° C 2.4 4.90 100 ° C 2.5 > 3.92 VV1 100 ° C 3.2 2.94 100 ° C 3.5 ⁇ 0.49 ⁇ 50 ° C 4-5 ⁇ 0.49 VV2 100 ° C 4.1 2.45 ⁇ 50 ° C > 6 - ⁇ 50 ° C - -
• Table 4 shows that the comparative compounds are no longer effective as curing agents at a bath temperature of> 38 ° C.
• the layers made with them begin to melt. This lowers the wet scratch resistance and increases swelling.
• a sample of the photosensitive member was exposed through a step wedge.
• the development took place in two steps; in the first, the photosensitive element was heated at 120 ° C for 60 s. This was done with the help of a heating plate, the sample being placed on the layer on the heating plate and covered with another plate.
• the sample was brought into contact with the image-receiving element on the layer side, the image-receiving element having previously been soaked with water.
• the set formed in this way was treated for 2 minutes at 70 ° C. using the same procedure as in the first step. During this time the color transfer took place the photosensitive member into the image receiving member.
• the two layer elements were then separated from one another. A purple negative image of the exposure original with high D max and low D min was obtained on the image receiving element.
• D max 2.02
• D min 0.19

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  • 1987-07-25 DE DE19873724672 patent/DE3724672A1/de not_active Withdrawn
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