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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/142—Dye mordant

Definitions

• the invention relates to a silver halide photographic material which contains at least one polypeptide copolymer.
• the polypeptide copolymers can perform different functions in the photographic material.
• Gelatin derivatives of degraded or hydrolyzed gelatin by reaction with anhydrides of polybasic acids are known as opacifiers.
• gelatin derivatives are also used which still contain C-C double bonds if the reaction is carried out with maleic anhydride or itaconic anhydride (DE-OS 2 129 758).
• Gelatin derivatives of i.a. enzymatically degraded gelatin by reaction with monofunctional compounds improve the wrinkle grain that occurs during rapid processing (DE-OS 2 407 347).
• N-vinylpyrrolidone graft polymers are described, which are obtained by polymerizing the N-vinyl pyrrolidones can be prepared in the presence of gelatin. It is disadvantageous that a considerable part of vinylpyrrolidone homopolymer is produced by this process.
• the object of the invention is to produce polymers which are produced by copolymerization, which contain polypeptide building blocks and which are not or only slightly contaminated by homopolymers.
• polypeptides are reacted with reactive monomers to form so-called peptide monomers, which are then converted in a conventional copolymerization process with ethylenically unsaturated compounds to give photographically useful polymers with polypeptide segments.
• copolymers with polypeptide segments 0.5 mg to 5 g / m2, preferably 2.5 mg to 1 g / m2, are used in particular in the photographic material.
• copolymers according to the invention with polypeptide segments hereinafter referred to as copolymers are used as peptizers for the preparation of photographic emulsions, as plasticizers, as polymeric couplers - if coupler monomers are copolymerized with the peptide monomers - as viscosity enhancers, etc. useful.
• copolymers according to the invention are distinguished by a significantly improved colloid stability.
• Polypeptides in the sense of this invention are condensation products of amino acids linked by peptide bonds in the form of an acid amide.
• the polypeptides have an average molecular weight Mw of 2,000 to 40,000, preferably 3,000 to 30,000.
• polypeptides can be carried out by the condensation of amino acids according to the known methods of peptide synthesis, as described, for example, in E. Wünsch, "Synthesis of Peptides” in Houben-Weyl, 4th ed. 1974 Georg Thieme Verlag.
• polypeptides can also be broken down by degrading higher molecular weight polypeptides, e.g. Proteins or proteins can be obtained by hydrolytic or enzymatic degradation.
• the enzymes pepsin, trypsin, chymotrypsin, papain and collagenase are particularly suitable for enzymatic degradation.
• the degradation can also take place hydrolytically.
• the protein or protein is in an aqueous solution with an acid at a pH of 0.1 to 1.0 or a base at a pH of 9.5 to 13.5 at temperatures of 50 to 70 ° C. heated.
• the molecular weights are determined by gel permeation chromatography.
• the molecular weight distribution is calculated using a calibration curve for polyethylene oxide or polystyrene sulfonic acid.
• Suitable proteins or proteins from which the polypeptides are obtained by hydrolysis are gelatin, collagen, keratin, albumins, globulins. Collagen or gelatin is preferably used for the hydrolytic degradation.
• polypeptides can also be synthesized by genetic engineering methods or by industrial microbiology.
• polypeptides required for the invention consist essentially of the amino acids glycine, alanine, serine, cysteine, phenylalanine, tyrosine, tryptophan, threonine, methionine, valine, proline, leucine, isoleucine, lysine, arginine, aspartic acid, asparagine, glutamic acid and glutamine.
• the polypeptides preferably contain glycine, proline, hydroxyproline, glutamic acid, alanine, arginine, aspartic acid and lysine.
• polypeptides which can be used according to the invention are more than 5% by weight soluble in water at pH 7 and 20 ° C. and, as a 20% by weight aqueous solution, have a viscosity of less than 20 mPa.s at 40 ° C. .
• a reactive group is understood to mean a group which is linked to -NH2-; -COOH or -OH groups of a polypeptide can react.
• Particularly preferred reactive groups are -COCl, -NCO, -Cl and -Br.
• the peptide monomers according to the invention are prepared by reacting the reactive monomers with the polypeptides in such a way that the reactive group X of the reactive monomer reacts with the polypeptide and the ethylenically unsaturated group is retained.
• the reaction is preferably carried out in the presence of polymerization inhibitors.
• the peptide monomers are purified by known methods, e.g. by accident or dialysis.
• polypeptide 2 50 g of polypeptide 2 are dissolved in 100 g of water, diluted with 50 ml of acetone and mixed with 0.5 g of di-t-butyl-p-cresol. At room temperature and a pH of 9, a solution of 2 g of R6 in 20 g of acetone is added dropwise over the course of 20 minutes. After stirring for 20 minutes, the solution is concentrated and Dripped minutes. After stirring for 20 minutes, the solution is concentrated and the peptide monomer is then precipitated with ethanol, suction filtered and washed with ethanol. Yield: 63% of theory
• copolymers according to the invention can contain one or more comonomers. Examples of comonomers are:
• Glyceryl methacrylate N ( m -hydroxyphenyl) methacrylamide, 2-hydroxyethyl acrylate, 2-phenyl-1-vinylimidazole, 2-hydroxypropyl acrylate, N-isopropylacrylamide, N- (1,1-dimethyl-3-dimethylaminopropyl) acrylamide, 2-methyl-1 vinylimidazole, 1-vinylimidazole, N-vinyl- ⁇ -caprolactam, p -Methansulfonamidostyrol, N-methyl methacrylamide, methacrylamide, N- (3-oxo-n butyl) maleimide, maleimide, N- (2-aminoethyl) methacrylamide, 2 -Hydroxyethyl methacrylate, methacryloyl urea, N- (3-aminopropyl) methacrylamide hydrochloride, N- (2-amino-2-methylpropyl) methacryl
• Suitable photographically useful groups are chemical structural elements that function as a UV absorber, a filter dye, a mordant, a development inhibitor, a developer, a bleaching agent, a bleaching inhibitor, a cyan, magenta or yellow coupler, a white coupler, a wetting agent, one Have DIR or DAR coupler, a mask coupler. Comonomers with these structures are described in US 5,234,807.
• copolymers of peptide monomer and comonomer according to the invention contain at least 3% by weight, preferably 10% by weight, of peptide monomer.
• the synthesis of the copolymers is described below.
• the copolymers according to the invention consist of 1 to 60% by weight of residues derived from the peptide monomer and 40 to 99% by weight of residues derived from comonomers.
• copolymer 1 (method 1) or copolymer 2 (method 2) (see table 2).
• copolymers according to the invention can be added to all layers of a photographic material; they are preferably added to the photosensitive silver halide emulsion layers, use in color photographic materials being preferred.
• the copolymers according to the invention are added to one or more of the precipitation solutions before or during the precipitation of the silver halides.
• the proportion of copolymer according to the invention is 0.01-50% by weight, preferably 0.05-10% by weight.
• the gelatin to silver weight ratio in the photographic material is preferably 0.3-1.5.
• the silver halide photographic material can be black and white or, preferably, color photographic materials.
• color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.
• Suitable supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or ⁇ -olefin polymer layer (e.g. polyethylene).
• These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
• the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
• the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
• Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.
• Gelatin is preferably used as the binder.
• this can also be completely or partially replaced by other synthetic, semisynthetic or naturally occurring polymers.
• Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
• Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
• Semi-synthetic gelatin substitutes are usually modified natural products. Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers are examples of this.
• the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
• functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
• the gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. High viscosity, low swelling gelatins are particularly advantageous.
• the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
• the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
• silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions. It can be predominantly compact crystals, e.g.
• platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being 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 substantially greater than 5: 1, e.g. 12: 1 to 30: 1.
• the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different.
• the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
• the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
• Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
• Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation of the silver halides and / or the physical ripening of the silver halide grains.
• the precipitation can also be carried out in the presence of sensitizing dyes.
• Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
• the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.
• the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
• the procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
• Chemical sensitization can take place with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium).
• Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Technical Chemistry, 4th edition, vol. 18, pp. 431 ff . and Research Disclosure 17643 (Dec. 1978), Chapter III).
• a reduction sensitization with the addition of reducing agents can be carried out by hydrogen through low pAg (eg less than 5) and / or high pH (eg above 8).
• the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
• Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Furthermore, salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
• metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
• Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
• mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.
• the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
• the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
• the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
• surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
• surface-active compounds e.g. Saponin
• non-ionic surfactants e.g. Alkylene oxide compounds, glycerin compounds or glycidol compounds
• cationic surfactants e.g.
• alkyl amines quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
• an acid group e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group
• ampholytic surfactants e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
• the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
• Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
• Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
• the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
• cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
• Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
• Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
• Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
• the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
• the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling.
• the 2-equivalent couplers include those that are colorless, as well as 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 (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
• the 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. as a development inhibitor or accelerator.
• Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
• the material may further contain compounds other than couplers, which can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
• couplers can liberate, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds as described, for example, in US Pat US-A-4 636 546, 4 345 024, 4 684 60
• 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 usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
• the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question.
• the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
• Hydrophobic compounds can also 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, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.
• oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
• the compounds can also be introduced into the casting solution in the form of loaded latices.
• anionic water-soluble compounds for example of dyes
• pickling polymers for example of cationic polymers
• Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
• Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
• red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers 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.
• the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
• the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
• sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
• the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity.
• Partial layers of the same spectral sensitization can be adjacent to one another or separated by other layers, for example by layers of different spectral sensitization.
• all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
• the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
• the layers of the photographic material can be hardened with the usual hardening agents.
• Suitable curing agents are e.g. 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 containing reactive halogen (US A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207), divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2
• the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
• Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction .
• Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
• hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
• Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
• All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol 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-methanesulfonamidoethyl) -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 G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
• bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
• Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulfates and peroxides e.g. Hydrogen peroxide.
• the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
• the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
• this stabilizing bath also acts as a final bath.
• Emulsion 1 (EM 1)
• the emulsion was then cooled, flocculated by acidification and with the addition of a flocculant.
• the flocculate was washed out several times and redispersed with the addition of inert bone gelatin, so that a silver / gelatin weight ratio of 1: 0.3 (based on silver nitrate) resulted.
• the emulsion thus obtained had an average grain diameter of 0.9 ⁇ m and an iodide content of 9.9 mol%.
• the proportion of tabular crystals in the total projection area was approx. 25% according to electron micrographs.
• the average aspect ratio of the tabular crystals was 3.5.
• EM1 is a comparison emulsion.
• EM 2 was prepared like EM 1 with the change that the template additionally contained 0.34 g of copolymer 1.
• the proportion of tabular crystals in the total projection area was 55% and the average aspect ratio of the tabular crystals was 6.
• EM 3 was produced like EM 1 with the change that the template additionally contained 1.36 g of copolymer 1.
• the proportion of tabular crystals in the total projection area was 78% and the average aspect ratio of the tabular crystals was 10.
• EM 4 was produced like EM 1 with the change that the template additionally contained 3.4 g of copolymer 1.
• the proportion of tabular crystals in the total projection area was 85% and the average aspect ratio of the tabular crystals was> 15.
• EM 5 was prepared like EM 1 with the change that the initial charge additionally contained 0.17 g of the compound PVP K30.
• the proportion of tabular crystals in the total projection area was 65% and the average aspect ratio of the tabular crystals was 7.
• EM 6 was prepared like EM 1 with the change that the initial charge additionally contained 0.68 g of the compound PVP K30.
• the proportion of tabular crystals in the total projection area was 80% and the average aspect ratio of the tabular crystals was 9.
• EM 7 was prepared like EM 1 with the change that the initial charge additionally contained 1.7 g of the compound PVP K30.
• the proportion of tabular crystals in the total projection area was 87% and the average aspect ratio of the tabular crystals was 17.
• PVP K30 is a polyvinyl pyrrolidone with Mw ⁇ 30,000.
• EM 8 was produced like EM 1 with the change that the initial charge additionally contained 0.34 g of copolymer 13.
• the proportion of tabular crystals in the total projection area was 45% and the average aspect ratio of the tabular crystals was 5.
• EM 9 was prepared like EM 1 with the change that the template additionally contained 1.36 g of copolymer 13. The proportion of tabular crystals in the total projection area was 72% and the average aspect ratio of the tabular crystals 11.
• EM 10 was produced like EM 1 with the change that the original contained an additional 3.4 g of copolymer 13.
• the proportion of tabular crystals in the total projection area was 78% and the average aspect ratio of the tabular crystals was> 12.
• EM 11 was produced like EM 1 with the change that the template additionally contained 0.34 g of the comparative polymer VP 1.
• the proportion of tabular crystals in the total projection area was 55% and the average aspect ratio of the tabular crystals was 6.5.
• EM 12 was produced like EM 1 with the change that the template additionally contained 1.36 g of the comparative polymer VP 1.
• the proportion of tabular crystals in the total projection area was 73% and the average aspect ratio of the tabular crystals was 8.
• EM 13 was produced like EM 1 with the change that the template additionally contained 3.4 g of the comparative polymer VP 1.
• the proportion of tabular crystals in the total projection area was 82% and the average aspect ratio of the tabular crystals was 15.
• Comparative polymer VP 1 is produced by polymerizing vinylpyrrolidone in gelatin solution.
• the weight ratio PVA: gelatin is 1.0.
• Emulsion 14 (EM 14)
• the emulsion was then cooled, flocculated by acidification and with the addition of a flocculant.
• the flocculate was washed out several times and redispersed with the addition of inert bone gelatin, so that a silver / gelatin weight ratio of 1: 0.3 (based on silver nitrate) resulted.
• the emulsion thus obtained had an average grain diameter of 0.8 ⁇ m and an iodide content of 3 mol%.
• the proportion of tabular crystals in the total projection area was approx. 35% according to electron micrographs.
• the average aspect ratio of the tabular crystals was 4.
• EM 14 is a comparative emulsion.
• EM 15 was produced in the same way as EM 14, except that the initial charge additionally contained 0.34 g of copolymer 1.
• the proportion of tabular crystals in the total projection area was 68% and the average aspect ratio of the tabular crystals was 7.5.
• EM 16 was produced like EM 14 with the change that the initial charge additionally contained 1.36 g of copolymer 1.
• the proportion of tabular crystals in the The total projection area was 84% and the average aspect ratio of the tabular crystals was 14.
• EM 17 was produced like EM 14 with the change that the original contained an additional 3.4 g of copolymer 1.
• the proportion of tabular crystals in the total projection area was 92% and the average aspect ratio of the tabular crystals was 18.
• EM 18 was prepared like EM 14 with the change that the initial charge additionally contained 0.17 g of the compound PVP K30.
• the proportion of tabular crystals in the total projection area was 73% and the average aspect ratio of the tabular crystals was 8.
• EM 19 was prepared like EM 14 with the change that the initial charge additionally contained 0.68 g of the compound PVP K30.
• the proportion of tabular crystals in the total projection area was 87% and the average aspect ratio of the tabular crystals was 16.
• EM 20 was prepared like EM 14 with the change that the initial charge additionally contained 1.7 g of the compound PVP K30.
• the proportion of tabular crystals in the total projection area was 94% and the average aspect ratio of the tabular crystals was 21.
• EM 21 was produced like EM 14 with the change that the template additionally contained 0.34 g of copolymer 3.
• the proportion of tabular crystals in the total projection area was 55% and the average aspect ratio of the tabular crystals was 6.
• EM 22 was produced like EM 14 with the change that the template additionally contained 1.36 g of copolymer 3.
• the proportion of tabular crystals in the total projection area was 78% and the average aspect ratio of the tabular crystals 11.
• EM 23 was produced like EM 14 with the change that the original contained an additional 3.4 g of copolymer 3.
• the proportion of tabular crystals in the total projection area was 80% and the average aspect ratio of the tabular crystals was 14.
• the further processing includes the following baths: Stop bath 1 minute at 38 ° C Bleach bath 3 1/4 minutes at 38 ° C Water 3 1/2 minutes at 38 ° C Fixer 3 1/4 minutes at 38 ° C Water 5 minutes at 38 ° C
• the stop, bleaching and fixing baths used correspond to those commonly used (British Journal of Photography, 1974 , pages 597 and 598).
• the sensitivity values of EM 2 to EM 13 relate to EM 1 (equal to 100), the sensitivity values from EM 15 to EM 23 relate to EM 14 (equal to 100).
• Table 3 shows that only the emulsions prepared with the compounds according to the patent have a spectral sensitizability which can be used for photographic use.
• the comparison compounds prevent effective spectral sensitization.
• the procedure is to add dropwise to 100 ml of the latex in a 250 ml beaker, 0.5 ml of the electrolyte solution or 100 ml of acetone with stirring and then to assess the latex stability.
• Comparative polymers 15A, 16A, 20A and 21A were prepared like copolymers 15, 16, 20 and 21 according to the invention, but without using peptide monomers 2 and 3.

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• 1994
  • 1994-02-07 DE DE4403683A patent/DE4403683A1/de not_active Withdrawn
• 1995
  • 1995-01-25 DE DE59508904T patent/DE59508904D1/de not_active Expired - Lifetime
  • 1995-01-25 EP EP95100961A patent/EP0666498B1/fr not_active Expired - Lifetime
  • 1995-01-27 US US08/380,019 patent/US5518877A/en not_active Expired - Fee Related
  • 1995-02-01 JP JP7034709A patent/JPH07225442A/ja active Pending

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