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

Definitions

• the invention relates to a light-sensitive silver halide photographic material, the gelatin layers of which have been hardened with a compound containing vinylsulfonyl groups.
• 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, such as anhydrides of tetracarboxylic acids, compounds with several reactive vinyl groups such as vinyl sulfones, acrylamides, compounds with at least 2 easily cleavable, heterocyclic 3-membered rings such as ethylene oxide and ethylene imine, polyfunctional methanesulfonic acid esters and bis-CC-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-
• high molecular weight curing agents such as polyacrolein or its derivatives or mixtures have been used polymers and alginic acid derivatives are known, which are used specifically as layer-limited curing agents.
• crosslinking agents for gelatin also have a skin-damaging effect, e.g. the ethyleneimine compounds, so that their use is not appropriate for physiological reasons alone.
• hardening agents for photographic gelatin layers are compounds with 2 or more acrylic acid amido groups in the molecule, N, N ', N "-trisacryloyl hydrotriazine or methylenebisacrylamide.
• the hardening of the compounds after some time is good, but the compounds are sparingly soluble in water, which can lead to irregularities in the hardening within the layer.
• DE-PS 1 100 942 aromatic vinyl sulfone compounds and DE-OS 1 547 733 nitrogen or oxygen as heteroatoms containing heterocyclic vinyl sulfone compounds are known.
• DE-PS 1 808 685 and DE-OS 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 them to be used in photographic gelatin layers, or they affect drying behavior of the layers disadvantageously. Other of these compounds increase the viscosity of the casting compositions so as to interfere with the processing of the casting compositions into layers.
• Known vinyl sulfone-type hardeners also cause migration of photographic additives from one layer to the other, particularly in color photographic recording materials, which causes color changes and those of the photographic properties.
• reaction products are known as curing agents which are obtained when reactions of compounds having at least 3 vinylsulfonyl groups in the molecule with compounds having a water-soluble group and a group which can react with a vinylsulfonyl group.
• Anionic vinylsulfonyl compounds are formed.
• these connections have disadvantages. They show strong post-curing in gelatin-containing photographic layers, i.e. their optimal effect only begins after the material has been stored for a long time. As a result, the layer swelling in the water decreases with increasing duration of storage and, as a result, the sensitometric data of the material change continuously.
• the known compounds after the known compounds have been added to the gelatin-containing silver halide emulsions, in particular at pH values around 7, the viscosity increases with increasing digestion time and this no longer permits an error-free pouring.
• the invention is based on the object of providing a hardening agent for photographic gelatin which has sufficient water solubility for this purpose, a hardening reaction which quickly comes to its optimum effect, and has no disruptive post-hardening effect.
• DE-PS 1 100 942 provides information about the production processes suitable for aromatic vinyl sulfone compounds.
• Heterocyclic vinylsulfonylalkyl compounds can be prepared in the manner described in DE-OS 1 547 733.
• the preparation of sulfonamide esters can be found in DE-A-1 094 735 and 1 178 071 or GB-PS 1 071 298.
• Information about the production of vinylsulfonylalkanes can be found in DE-OS 2 348 194.
• the following compounds (B) are, for example, suitable as amines which can be reacted with the vinylsulfonyl group-containing compounds (A) as amine salts, such as chlorides or sulfates:
• the amines of formula (B) are commercially available products.
• the curing agents according to the invention - hereinafter referred to as (C) - contain at least 2 vinylsulfonyl groups and at least one group obtained by reacting a vinylsulfonyl group with an amine (compounds (B)) in the molecule.
• the reaction products are water-soluble and have excellent crosslinking properties for gelatin-containing layers.
• the compounds (C) are obtained by reacting the solutions of the compounds (A) with solutions of the compounds (B) in the form of their amine salts or as free amines, in the latter case the amines being converted into the amine salts after the reaction has ended, for example by addition corresponding amounts of an acid such as HCl or H 2 S0 4 .
• the molar ratios of the vinylsulfonyl compounds and amines in the reaction vary depending on the number of vinylsulfonyl groups of the compounds (A). Basically, the reaction product contains at least two unreacted vinyl sulfone groups. 1 mol of compound (A) is preferably reacted with 0.5-1 mol of compound (B).
• reaction products are preferably used as they are after the reaction, i.e. without isolating them. However, the reaction products can also be isolated and purified.
• the cationic compounds of the invention are generally used as curing agents as they are obtained in the production process. However, if the purpose so requires, they can also be used in more dilute or concentrated solutions. Incidentally, the hardening of the gelatin with the hardening agents of the invention can be carried out according to all methods customary for this.
• the hardeners are generally incorporated into the casting solutions in an amount of 0.01 to 100% by weight and preferably 0.1 to 10% by weight, based on the dry weight of the gelatin.
• the timing of the addition is not critical.
• Silver halide emulsions will expediently add the hardener after chemical ripening.
• the hardening agent can of course also be introduced in the form of a solution using the so-called overlay process in a layered structure.
• photographic layers are to be understood very generally as layers which are used in the context of photographic materials, for example light-sensitive silver halide emulsion layers, protective layers, filter layers, antihalo layers, backing layers or very generally photographic auxiliary layers.
• emulsion layers for which the curing method according to the invention is excellently suitable, there may be mentioned, for example, layers which are based on non-sensitized emulsions, X-ray emulsions and other spectrally sensitized emulsions.
• the hardening has also proven itself Process of the invention for curing the gelatin layers used for the various black-and-white and color photographic processes such as negative, positive and diffusion transfer processes or printing processes.
• the method according to the invention has proven to be particularly advantageous for the hardening of photographic layer dressings which are intended for carrying out color photographic processes, for example those which contain emulsion layers with color couplers or emulsion layers which are intended for treatment with solutions which contain color couplers.
• the effect of the compounds used in the manner according to the invention is not impaired by the usual photographic additives.
• the hardening agents are also indifferent to photographically active substances, e.g. water-soluble and emulsified water-insoluble color components, stabilizers and sensitizers. Furthermore, they have no adverse effect on the light-sensitive silver halide emulsions.
• the emulsion layers can be any known silver halide, e.g. Contain silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide and silver chlorobiodobromide.
• the emulsions can be chemically sensitized by noble metal compounds, e.g. through compounds of ruthenium, rhodium, palladium, iridium, platinum, gold,
• Ammonium chloropalladate, potassium chloroplatinate, potassium chloropalladite, or potassium chloroaurate can also contain special sensitizers for sulfur compounds, tin (II) salts, polyamines or polyalkylene oxide compounds.
• the emulsions can be optically sensitized with cyanine dyes, merocyanine dyes and mixed cyanine dyes.
• the emulsions can be a variety of couplers, e.g. colorless couplers, colored couplers, stabilizers such as mercury compounds, triazole compounds, azainden compounds, benzothiazolium compounds or zinc compounds, wetting agents such as dihydroxyalkanes, agents which improve the film-forming properties, e.g.
• the water-dispersible, particulate high polymers obtained in the emulsion polymerization of alkyl acrylate or alkyl methacrylate / acrylic acid or methacrylic acid mixed polymers, styrene / maleic acid mixed polymers or styrene / maleic anhydride semi-alkyl ester mixed polymers, coating aids, such as polyethylene glycol astenyl ether acrylates, as well as additives.
• the hardening agents of the invention do not have the property of suddenly having their hardening effect, nor do they tend to over-harden gelatin layers. Both properties represent a major advantage for the manufacturing process of photographic materials.
• the layered structure is then dried.
• the photographic film thus produced serves as a comparison material in the following.
• the production of the film is repeated, with the individual layers per film sample being each one of the curing agents C / 1, C / 2, C / 3, C / 4, C / 11 and C / 15 in an amount of 0.02 g per gram of gelatin.
• test specimen is developed as a black sheet in a conventional color development process and weighed after the final bath after the excess water has been stripped off. The sample is then dried and weighed again. The difference from the area of the test object to 1 m 2 converts the water absorption per m 2 .
• 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.
• Table 1 shows, excellent curing is obtained with the curing agents of the invention.
• the melting points of the layers are above 100 ° C and the wet scratch resistance values are so high that processing in machines is possible.
• the viscosities of the casting solutions do not increase within one hour of digestion at 40 ° C. Also, the hardening effect does not start suddenly, as can be seen from the increase in the crosslinking of the layers after longer storage at 30 ° C., 80% rel. Humidity results.
• 1, 2 and 5 g of the compounds according to the invention are added to 100 g of gelatin in the form of the aqueous solutions at pH 6.2 to 100 ml of ready-to-pour photographic silver bromide gelatin emulsion which contains 10% by weight of gelatin.
• the mixtures are stirred well and poured onto a prepared cellulose triacetate base using a conventional casting machine and dried. The usual additions are not changed. Details regarding the composition of the samples, the various test conditions and finally the results are summarized in Table 3 below. As Table 3 shows, the crosslinking increases with increasing amount of curing agent, but no overcuring is obtained (this would mean, for example, swelling factors ⁇ 2 or wet scratch resistance> 1000). Post-curing also decreases with an increasing amount of curing agent.
• the layer melting point 100 ° C. is obtained with some of the compounds according to the invention after standing for 1 day with the exclusion of air at 22 ° C., a sign of a relatively rapid and uniform crosslinking. All photographic properties are preserved. Veil and sensitivity are not changed. Liability on the pad is good.
• the example shows the differences in the reaction of the compounds according to the invention to the known curing agents.
• the curing agents to be tested were each used in a black and white photographic emulsion.
• the emulsion had the composition
• the known hardeners served as comparison compounds (VV): Compound C / 1 was used as the curing agent according to the invention. 2% by weight hardener based on gelatin was added to the casting solutions. The casting solutions were poured onto a cellulose triacetate support provided with an adhesive layer and dried (layer thickness 10 ⁇ ).
• the hardening properties were measured after different storage times under different climatic conditions. The results are shown in Table 4 below.
• Table 4 shows that the comparative samples VV1 and VV2 harden strongly during long-term storage.
• the swelling factors are initially relatively high and decrease significantly after long-term storage. This lowers the maximum densities of the developed film samples (slowed through development or reduced silver opacity). If you are aiming for materials that show good developability and medium hardening after long-term storage, it is necessary to use fewer hardening agents. However, one then has to accept the disadvantage of having strongly swelling, ie too soft, photographic layers available for shorter storage times.
• the compound 'C / 1 according to the invention used for comparison cures the material relatively quickly to a medium degree of hardening and then shows only insignificant post-hardening in the case of long-term storage.
• the hardeners of the invention thus give a balanced hardening of the photographic material, which is largely independent of the storage.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1979
  • 1979-10-30 DE DE19792943806 patent/DE2943806A1/de not_active Withdrawn
• 1980
  • 1980-10-20 EP EP80106379A patent/EP0027988B1/fr not_active Expired
  • 1980-10-20 DE DE8080106379T patent/DE3060375D1/de not_active Expired
  • 1980-10-27 US US06/201,210 patent/US4349624A/en not_active Expired - Lifetime
  • 1980-10-28 CA CA000363448A patent/CA1146000A/fr not_active Expired

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