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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/392—Additives
  • G03C7/39204—Inorganic compounds

Definitions

• the invention relates to a color photographic recording material which contains at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive silver halide-containing binder layer on a reflective layer support and optionally further non-light-sensitive binder layers, the binder of which is hardened with an instant hardener.
• the hardeners generally react with free amino, imino or hydroxyl groups of the proteinaceous binder with crosslinking thereof.
• slow-reacting hardeners are disadvantageous in that, for example, important parameters of the cast layers in photographic recording materials change with increasing storage time to change.
• sensitometric data such as sensitivity, gradation and maximum density can drift slowly and the final properties of the layer or layer structure are often only achieved after a considerable period of storage. This necessitates increased testing effort during production.
• fast-acting hardening agents because with them the final properties are achieved within a short time after the casting, so that the required storage or waiting times can be shortened and the testing effort can be reduced.
• Very useful fast-acting curing agents hereinafter also called instant hardeners, are described in DE-A-22 25 230, DE-A-23 17 677 and DE-A-24 39 551.
• Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed immediately after casting or at the latest after 24 hours, preferably after 8 hours, to the extent that no further change in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs.
• Swelling is understood to mean the difference between the wet layer thickness and the dry layer thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. 16 (1972), 449).
• hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which presumably are able to react with free carboxyl groups of the proteinaceous binder, so that the latter can react with free amino groups to form peptide bonds and crosslink the binder.
• carbamoylpyridinium salts which presumably are able to react with free carboxyl groups of the proteinaceous binder, so that the latter can react with free amino groups to form peptide bonds and crosslink the binder.
• the instant hardeners mentioned may generally only be added to casting solutions containing gelatin shortly before the casting, since otherwise the casting properties, in particular the viscosity of the casting solutions, would be changed quickly and sustainably by premature reaction.
• the immediate hardener is added to the top layer (protective layer). By diffusion it reaches the other gelatin-containing layers to be hardened and crosslinks the gelatin so quickly that the hardening is almost complete after drying and the parameters characteristic of the physical and photographic properties have reached their final values.
• a disadvantage of using instant hardeners is an increase in the formation of fog both with fresh materials and after storage.
• the invention had for its object to provide a color photographic recording material which is produced using instant hardeners, but nevertheless shows an extraordinarily low haze with otherwise unchanged good sensitometric properties both when fresh and after storage.
• the invention therefore relates to a color photographic recording material of the type mentioned at the outset which contains either 100 to 900 mmol of soluble chloride and 0 to 50 mmol of soluble bromide / mol of Ag or 0 to 600 mmol of soluble chloride and 5 to 50 mmol of soluble bromide / mol of Ag.
• the soluble halide is preferably added to the blue-sensitive layer or the blue-sensitive layers or one or more layers free of silver halide adjacent to the blue-sensitive layers.
• the amount of soluble chloride is preferably 300 to 600 mmol / mol Ag.
• the instant hardener is used in an amount of 0.1 to 5 mmol / m2, preferably 0.5 to 1.7 mmol / m2.
• the soluble halides are preferably in the form of an alkali, alkaline earth metal or ammonium halide, e.g. B. NH4BR, NH4Cl, NaBr, NaCl, KBr, KCl or LiCl, at least one photosensitive silver halide emulsion layer.
• an alkali, alkaline earth metal or ammonium halide e.g. B. NH4BR, NH4Cl, NaBr, NaCl, KBr, KCl or LiCl, at least one photosensitive silver halide emulsion layer.
• Suitable examples of instant hardeners are compounds of the following general formulas: wherein R1 denotes alkyl, aryl or aralkyl, R2 has the same meaning as R1 or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula is linked, or R1 and R2 together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted, for example, by C1-C3alkyl or halogen, R3 for hydrogen, alkyl, aryl, alkoxy, -NR4-COR5, - (CH2) m -NR8R9, - (CH2) n -CONR13R14 or - (CH2) p - Y-R16 or a bridge link or a direct bond to a polymer chain, wherein R4, R6, R7, R9, R14, R15
• the heteroaromatic ring represented by R51 is, for example, a triazole, thiadiazole, oxadiazole, pyridine, pyrrole, quinoxaline, thiophene, furan, pyrimidine or triazine ring. In addition to the at least two vinylsulfonyl groups, it may optionally contain further substituents and optionally fused-on benzene rings, which in turn may also be substituted. Examples of heteroaromatic rings (R51) are listed below. wherein r is a number from 0 to 3 and R52 is C1-C4-alkyl, C1-C4-alkoxy or phenyl.
• alkyl is in particular C1-C2 Hydrox-alkyl optionally substituted by halogen, hydroxy, sulfo, C1-C20-alkoxy.
• Aryl unless otherwise defined, is in particular optionally substituted by halogen, sulfo, C1-C20-alkoxy or C1-C20-alkyl C6-C14-aryl.
• Aralkyl unless otherwise defined, is in particular C Halogen-C20-aralkyl substituted by halogen, C1-C20-alkoxy, sulfo or C1-C20-alkyl.
• Alkoxy unless otherwise defined, is in particular C1-C20 alkoxy.
• X ⁇ is preferably a halide ion such as Cl ⁇ , Br ⁇ or BF4 ⁇ , NO3 ⁇ , (SO4 2 ⁇ ) 1/2 , ClO4 ⁇ , CH3OSO3 ⁇ , PF6 ⁇ , CF3SO3 ⁇ .
• Alkenyl is especially C2-C20 alkenyl.
• Alkylene is especially C2-C20 alkylene; Arylene especially phenylene, aralkylene especially benzylene and alkaralkylene especially xylylene.
• Suitable N-containing ring systems that can represent Z are shown on the previous page.
• the pyridine ring is preferred.
• R36 and R37 together with the nitrogen atom to which they are attached, in particular form a pyrrolidine or piperidine ring bonded by 2 oxo groups in the o- and o ⁇ -position, which may be benzo, cyclohexeno- or [2.2.1] -bicyclohexenocondensed.
• Acyl is especially C1-C10 alkylcarbonyl or benzoyl; Carbalkoxy is especially C1-C10 alkoxycarbonyl; Carbamoyl is especially mono- or di-C1-C4 alkylaminocarbonyl; Carbaroxy is especially phenoxycarbonyl.
• Groups R24 which can be split off by nucleophilic agents are, for example, halogen atoms, C1-C15 alkylsulfonyloxy groups, C7-C15 aralkylsulfonyloxy groups, C6-C15 arylsulfonyloxy groups and 1-pyridinyl radicals.
• the compounds can be prepared in a simple manner known from the literature.
• the secondary amines are e.g. with phosgene, the carbamic acid chlorides, which are then reacted with aromatic, heterocyclic nitrogen-containing compounds in the dark.
• the preparation of compound 3 is described in Chemical Reports 40, (1907), page 1831. Further information on the synthesis can be found in DE-OS 2 225 230, DE-OS 2 317 677 and DE-OS 2 439 551.
• JP-OSs 44 140/82 and 46 538/82 and JP-PS 50 669/83 Methods for the synthesis of these compounds are described in more detail in JP-OSs 44 140/82 and 46 538/82 and JP-PS 50 669/83.
• the compounds (a) are particularly preferred.
• the binder to be cured used in the layers which are subjected to the curing process according to the invention is a proteinaceous binder which contains free amino groups and free carboxyl groups.
• Gelatin is a preferred example. Gelatin is mainly used in photographic recording materials as a binder for the light-sensitive substances, the coloring compounds and, if appropriate, other additives. Such recording materials often have a large number of different layers.
• the hardening by means of an immediate hardener is usually carried out in such a way that the hardening agent is applied in excess as the last layer on the layers to be hardened gene, wherein the hardening coating solution further substances such as UV absorbers, antistatic agents, matting agents and polymeric organic particles can be added.
• the layer containing the hardening agent can be applied simultaneously with or after the casting of the remaining layers by means of cascade or curtain coaters.
• the casting temperature can be varied over a wide range, e.g. B. between 45 and 5 ° C, preferably between 38 and 18 ° C.
• the layer thickness of the hardening casting is, for example, between 0.2 and 2.5 ⁇ m.
• Other additives such as UV absorbers, color correction dyes, antistatic agents and inorganic or organic solid particles, which are used, for example, as matting agents or spacers, can be added to the hardener-containing layer.
• Suitable UV absorbers are described, for example, in US Pat. No. 3,253,921, DE-C-20 36 719 and EP-A-0 057 160.
• suitable inorganic solid particles are silicon dioxide, magnesium dioxide, titanium dioxide and calcium carbonate. Such materials are widely used to matt the outermost layers of photographic recording materials and thus reduce their stickiness. Also fixed part Chen organic nature, which can be alkali-soluble or alkali-insoluble, are suitable for this purpose. Such particles, also referred to as spacers, generally roughen the surface, so that the surface properties, in particular the adhesive or sliding properties, can be modified thereby. Polymethyl methacrylate is an example of alkali-insoluble spacers. Alkali-soluble spacers are described, for example, in DE-A-34 24 893. Particulate organic polymers with reactive groups, in particular those reactive groups which react with the binder, as described, for example, in DE-A-35 44 212, can also be added as so-called hardeners.
• the hardener-containing partial layer which contains comparatively little or no binding agent
• its thickening agent such as polystyrene sulfonic acid or hydroxyethyl cellulose.
• the color photographic recording materials according to the present invention are multilayer materials which have a plurality of silver halide emulsion layers or emulsion layer units with different spectral sensitivity.
• the emulsion layer unit is understood to be laminates of 2 or more silver halide emulsion layers of the same spectral sensitivity. Layers of the same However, spectral sensitivity does not necessarily have to be arranged adjacent to one another, but can also be separated from one another by other layers, in particular also by layers of different spectral sensitivity.
• the binder in these layers is usually a protein-like binder with free carboxyl groups and free amino groups, preferably gelatin.
• the layered binder can contain up to 50% by weight of non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives and gelatin derivatives.
• non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives and gelatin derivatives.
• each of the light-sensitive silver halide emulsion layers or emulsion layer units mentioned is assigned at least one coloring compound, usually a color coupler, which can react with color developer oxidation products to form a non-diffusing dye.
• the color couplers are expediently non-diffusing and accommodated in the light-sensitive layer itself or in close proximity to it.
• the color couplers assigned to the two or more partial layers of an emulsion layer unit do not necessarily have to be identical. They are only intended to give the same color in color development, usually a color that is complementary to the color of the light to which the photosensitive silver halide emulsion layers are sensitive.
• the red-sensitive silver halide emulsion layers are consequently 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.
• a coupler of the phenol or ⁇ -naphthol type usually a coupler of the phenol or ⁇ -naphthol type.
• Particularly noteworthy are, for example, cyan couplers as described in US-A-2,474,293, US-A-2,367,531, US-A-2,895,826, US-A-3,772,002, EP-A-0 028 099 , EP-A-0 112 514.
• the green-sensitive silver halide emulsion layers are generally assigned at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used. Cyanoacetyl compounds, oxazolones and pyrazoloazoles are also suitable as magenta couplers. Particularly noteworthy are, for example, purple couplers, as described in US Pat. Nos. 2,600,788, 4,383,027, 1,547,803, 1,810,464, 24,066,665, DE -A-32 26 163 are described.
• the blue-sensitive silver halide emulsion layers are normally assigned at least one non-diffusing color coupler to produce the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
• a color coupler with an open-chain ketomethylene grouping are particularly noteworthy.
• yellow couplers as described in US Pat. No. 3,408,194, US Pat. No. 3,933,501, DE-A-23 29 587, DE-A-24 56 976.
• Color couplers of these types are known in large numbers and are described in a large number of patents. Examples include the publications “Color Coupler” by W. Pelz, "Messages from the research laboratories of Agfa, Leverkusen / Kunststoff", Volume III (1961) p. 111, and by K. Venkataraman in “The Chemistry of Synthetic Dyes” , Vol. 4., 341 to 387, Academic Press (1971).
• 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 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 (mask coupler).
• the known white couplers are also to be counted among the 2-equivalent couplers, but they essentially result in colorless products on reaction with color developer oxidation products.
• the 2-equivalent couplers are also those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and which 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, for example as a development inhibitor or accelerator, examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or FAR couplers.
• Suitable DIR couplers are for example in GB-A-953 454, DE-A-1 800 420, DE-A-20 15 867, DE-A-24 14 006, DE-A-28 42 063, DE-A- 34 27 235.
• Suitable DAR or FAR couplers are described, for example, in DE-A-32 09 110, EP-A-0 089 834, EP-A-0 117 511, EP-A-. 0 118 087.
• DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, the products which are essentially colorless upon coupling, as described, for example, in DE-A-1 547 640.
• the cleavable residue can also be a ballast residue, so that when reacting 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, as described, for example, in US Pat. No. 4,420,556.
• 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-0 027 284, 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 layers of the color photographic recording material to be hardened by the process according to the invention may contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
• the layers to be hardened can also contain compounds which absorb UV light.
• Sample 1 The material thus obtained was referred to as Sample 1 (comparison).
• Another material was prepared in an analogous manner, with the difference that, after sensitization and stabilization, 37 mmol of KBr / mol of Ag were added to the blue-sensitive emulsion (sample 2).
• Example 1 A material was prepared according to Example 1 (Sample 1), but with the difference that 10 mmol KBr / mol Ag were added to the blue-sensitive emulsion after sensitization and stabilization.
• Example 1 The same compounds as in Example 1 were used as color couplers, UV absorbers and hardeners.
• Sample 1 The material thus obtained was referred to as Sample 1 (comparison).
• Sample 2 Another material was prepared in an analogous manner, with the difference that after sensitization and stabilization, 580 mmol NaCl / mol Ag were added to the blue-sensitive emulsion (Sample 2). As can be seen from the table, the fresh and stored veil is reduced by the measure according to the invention.

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• 1987
  • 1987-04-11 DE DE19873712426 patent/DE3712426A1/de not_active Withdrawn
• 1988
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