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
  • G03C7/32—Colour coupling substances
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
• • 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
• • 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
  • G03C7/32—Colour coupling substances
  • G03C7/36—Couplers containing compounds with active methylene groups
  • G03C7/38—Couplers containing compounds with active methylene groups in rings
  • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

• the invention relates to a light-sensitive color photographic recording material with a light-reflecting layer support and at least three light-sensitive silver halide emulsion layers of different spectral sensitivity arranged thereon, to which a cyan coupler, a magenta coupler and a yellow coupler are each spectrally assigned and which are hardened with a carboxyl group-activating hardening agent.
• a cyan coupler, a magenta coupler and a yellow coupler are each spectrally assigned and which are hardened with a carboxyl group-activating hardening agent.
• the diverse requirements which are placed on the color couplers also include the property of producing the lowest possible color fog (Dmin) during color development.
• Dmin color fog
• 2-equivalent couplers are often used to generate the yellow partial color image, which are derived from pivaloylactanilide.
• the invention is based on the object of specifying a color photographic recording material containing silver halide and color couplers, the binder layers of which are hardened with a carboxyl group-activating hardening agent, and by means of which chromogenic development enables colored top images to be produced with the least possible fog (Dmin) of the yellow partial color image. It has been found that when a special group of 2-equivalent yellow couplers derived from pivaloylacetanilide is used, a yellow partial color image with very little fog is obtained by additionally using white couplers,
• An oxygen-bonded group represented by X in formula II corresponds to the formula -OR, in which R stands for a cyclic organic radical.
• R stands for a cyclic organic radical.
• R is an optionally substituted phenyl group. Examples of this are described in US-A-3 408 194.
• cleavable groups X which are attached via nitrogen are described in the following German Offenlegungsschriften (DE-A-): 20 57 941, 21 63 812, 22 13 461, 22 19 917, 22 61 361, 22 63 875, 23 18 807, 23 29 587, 23 44 155, 23 63 675, 24 33 812, 24 41 779, 24 42 703, 25 28 638, 25 28 860, 26 37 817, 28 18 373, 28 42 063, 30 20 416.
• DE-A- German Offenlegungsschriften
• heterocyclic rings which are connected to the coupling point of the pivalylacetanilide coupler via a ring nitrogen atom.
• the heterocyclic rings often contain groups adjacent to the nitrogen atom activating binding to the coupler molecule, e.g. Carbonyl or sulfonyl groups or double bonds.
• the cleavable group represented by X is bonded to the coupling site of the coupler via a sulfur atom, it can be the residue of a diffusible mercapto compound which is able to inhibit the development of silver halide.
• inhibitor residues are often found at the coupling site of couplers bound cleavable group has been described, for example in US-A-3,227,554.
• An alkoxy group represented by Y in formula II is preferably one having a short alkyl radical, for example having up to 4 carbon atoms; Methozy is a good example of this.
• An alkyl group represented by R4 in formula II can be unsubstituted or substituted, straight-chain or branched. It is preferably an alkyl group which is a ballast radical or contains a substituent. Such an alkyl group can, for example, contain up to 20 carbon atoms and / or be substituted with aroxy.
• a substituent represented by R5 in Formula III usually contains a ballast residue; however, one of the substituents represented by S may also contain a ballast residue. Accordingly, for example, an alkyl, alkoxy or acylamino group represented by R5 can contain a longer aliphatic radical with up to 20 C atoms or be substituted accordingly.
• An amino group represented by R5 likewise comprises one or two, e.g. alkyl, aralkyl or aryl (anilino) substituted, as well as cyclic amino groups such as pyrrolidino.
• An anilino group represented by R5 in formula III may be further substituted in a conventional manner, e.g.
• acylamino group represented by R5 in formula III contains an acyl residue which can be derived from aliphatic or aromatic carboxylic or sulfonic acids or from carbamic acids (urea) or carbonic acid monoesters (urethane).
• An alkyl group represented by R6 in formula III preferably contains no more than 6 carbon atoms; they can also be substituted, for example by -CN, alkoxycarbonyl, alkoxy or acetyl.
• a substituent represented by S in formula III is preferably an alkylsulfonyl group, especially a group -SO2-CH3. If there are several substituents S (up to 3), they do not necessarily have to be identical.
• a substituent represented by S can also be an acylamino group, where the acyl radical can be derived equally from preferably aliphatic carboxylic or sulfonic acids.
• At least one predominantly blue-sensitive, one predominantly green-sensitive and one predominantly red-sensitive silver halide emulsion layer are layered one on top of the other on a layer support. If the blue-sensitive layer is arranged at the top of the layer structure, there can be a layer with a yellow filter dye underneath and above the green- or red-sensitive layers. Furthermore, intermediate layers can be arranged between two silver halide emulsion layers of different spectral sensitivity.
• the predominantly blue-sensitive silver halide emulsion layer contains a yellow coupler
• the predominantly green-sensitive silver halide emulsion layer contains a magenta coupler
• the predominantly red-sensitive silver halide emulsion layer contains a cyan coupler.
• the light-sensitive layers are on an opaque light-reflecting layer
• Layer supports are layered, for example on a layer support made of paper, which can carry a barite layer and / or can be covered on one or both sides with a layer made of a polyolefin.
• the photographic material of the present invention may contain one or more polymers as a binder for the silver halide and the color couplers.
• a common binder is gelatin.
• Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinyl-pyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular 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 generally 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.
• cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose
• gelatin derivatives obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers are examples of this.
• functional groups are particular Amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
• the preferred binder of the color photographic recording material according to the invention is gelatin.
• the binder layers of the recording material according to the invention are hardened with a hardening agent of the formula I.
• a hardening agent of the formula I Such curing agents are described for example in DE-A-24 39 551. Examples of such curing agents (H-) are listed below:
• the recording material according to the invention contains a 2-equivalent yellow coupler of the general formula II in the blue-sensitive silver halide emulsion layers. Examples of these are listed below (Y-); the yellow couplers contain the following cleavable groups: Examples of white couplers suitable according to the invention are listed below.
• the white coupler is advantageously used either in the same layer and / or in an adjacent layer which need not be light-sensitive. These adjacent layers can be arranged both above and below the respective blue-sensitive silver halide emulsion layer. It is also possible for the white coupler to be contained in both adjacent layers. If, for example, the blue-sensitive layer containing the yellow coupler according to the invention is arranged as the lowermost light-sensitive layer on the layer support, then the white coupler can be in this layer, or in a binder layer arranged between this layer and the layer support, e.g. an adhesive or antihalation layer, or in an adjacent protective layer arranged above the blue-sensitive layer, or in several or all of these layers.
• the incorporation of the yellow couplers and the white couplers as well as the other compounds to be introduced can be carried out by first preparing a solution or a dispersant from the compound in question and then adding it to the casting solution for the layer in question.
• 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. Appropriate 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 light-sensitive silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide.
• the halide content of at least one layer consists of 0 to 12 mol% of iodide, 0 to 50 mol% of chloride and 50 to 100 mol% of bromide.
• the halide can also consist predominantly of chloride.
• the crystals are predominantly compact, for example cubic or octahedral or have transition forms. They can be characterized in that 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.
• all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.
• the emulsions can be monodisperse emulsions which preferably have an average grain size of 0.3 ⁇ m to 1.2 ⁇ m.
• the silver halide grains can have a layered grain structure.
• the emulsion can be chemically and or spectrally sensitized in the usual way and can contain stabilizers.
• Suitable chemical sensitizers, spectral sensitizing dyes and stabilizers are described, for example, in Reasearch Disclosure 17643; Reference is made in particular to chapters III, IV and VI.
• the color photographic recording material according to the invention for producing multicolored images contains, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, color couplers for producing the different partial color images cyan, purple and yellow.
• Spatial assignment is to be 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 permits 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 an adjacent, if appropriate, non-light-sensitive binder layer.
• Spectral assignment is to be 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 in a certain relationship to one another stand, each of the spectral sensitivities (red, green, blue) is assigned a different color of the partial color image in question (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 several silver halide emulsion layers of the same spectral sensitivity are present, 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 various pyrazoloazole type usually being used; such pyrazoloazoles are described, for example, in DE-A-35 16 996.
• blue-sensitive silver halide emulsion layers is at least one non-diffusing Color couplers assigned to the generation of the yellow partial color image, in the present case a yellow coupler of the general formula II, color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publications “Color Coupler” by W. PELZ in “Messages from the Research Laboratories of Agfa, Leverkusen / Kunststoff", Volume III, page 111 (1961) and by K.VERKATARAMAN in "The Chemistry of Synthetic Dyes", Vol 4, 341 to 387, Academic Press (1971).
• the color couplers of the green or red-sensitized silver halide emulsion layers can be either conventional 4-equivalent couplers or 2-equivalent couplers, in which a smaller amount of silver halide is required to produce the color.
• 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling.
• the 2-equivalent couplers include the known white couplers (and thus also the compounds of the general formula III), which, however, do not give any dye when reacted with color developer oxidation products.
• the 2-equivalent couplers are also the known DIR couplers, which are couplers which contain a detachable radical in the coupling point, which acts as a diffusing development inhibitor in reaction with color developer oxidation products is set free.
• the couplers, including the compounds of the formula II used according to the invention can also be used in polymeric form, for example as polymer latex.
• 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 2111.
• the high molecular weight color couplers are generally produced by polymerizing ethylenically unsaturated monomeric color couplers .
• the BALL group then contains a segment of a polymer backbone.
• the color couplers that have died can also be those that have dyes with a weak bze. deliver limited mobility.
• the color photographic recording material of the present invention may contain further additives, such as, for example, antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
• antioxidants such as, for example, antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
• dye-stabilizing agents such as, for example, dye-stabilizing agents for influencing the mechanical and electrostatic properties.
• UV absorbers are described for example in US-A-3 253 921, DE-C-2 036 719 and EP-A-0 057 160.
• the color photographic recording material according to the invention which, in association with at least one silver halide emulsion layer, contains a combination of at least one yellow coupler of the formula II and at least one white coupler of the formula III, is developed with a color developer compound.
• All developer compounds which have the ability in the form of their oxidation product to react with color couplers to form azomethine dyes can be used as the color developer compound.
• Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type which contain 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-hydroxyethyl) -3-methyl-p-phenylenediamine.
• N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-eth
• Sample 1 The material thus obtained was referred to as Sample 1 (comparison).
• Another material was produced in an analogous manner, with the difference that 20 mg of compound W-11, emulsified with 20 mg of tricresyl phosphate, and 6 mg of compound W in the blue-sensitive layer (layer 3) in the adhesive layer (layer 2) -11 were additionally stored.
• This material was designated sample 2 (according to the invention).
• Example 3 According to the information in Example 1, further materials were produced (samples 3 to 6), which differ from sample 1 as follows:
• sample 3 serves as a comparison for sample 4
• Sample 6 contains no white coupler in layers 3 - 6 and thus serves as a comparison for sample 5 This means that another hardener not according to the invention was used (sample 4) or another white coupler, also according to the invention, was used (sample 5).
• Table 2 The result is shown in Table 2, in which the yellow veil Dmin, gb of the unsupported (fresh) material and the increase in the yellow veil ⁇ Dmin after storage are given for each of the materials.

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• Chemical Kinetics & Catalysis (AREA)
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• 1986
  • 1986-08-02 DE DE19863626221 patent/DE3626221A1/de not_active Withdrawn
• 1987
  • 1987-07-21 DE DE8787110513T patent/DE3779830D1/de not_active Expired - Fee Related
  • 1987-07-21 EP EP87110513A patent/EP0255892B1/de not_active Expired - Lifetime
  • 1987-07-31 JP JP62190524A patent/JPS6338932A/ja active Pending

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