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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
• • 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
  • Y10S430/156—Precursor compound
  • Y10S430/16—Blocked developers

Definitions

• the invention relates to a color photographic recording material having at least one light-sensitive silver halide emulsion layer which contains non-diffusing electron donor precursor compounds from which strong reducing agents are formed under the conditions of alkaline development.
• the invention relates to a recording material in which the electron donor precursor compounds mentioned are used in combination with non-diffusing reducible coloring compounds which, in the reduced state under the conditions of alkaline development, release diffusible dyes, which as such or after conversion into their metal complexes for image formation serve.
• DE-OS 2 809 716 describes coloring compounds with an electron-accepting nucleophilic precursor group, which in the reduced state are subject to an intramolecular nucleophilic displacement reaction under the conditions of alkaline development with the release of a diffusible dye.
• ED compounds electron donor compounds
• the remaining imagewise distribution (positive residual image) of the ED compounds reacts with the coloring compound and triggers the imagewise release of diffusible dyes.
• the ED compounds described there are, for example, derivatives of benzisoxazolone, hydroquinone, p-aminophenol and ascorbic acid.
• the ED compounds In order to enable the generation of high-quality images by the process described in DE-OS 2 809 716, the ED compounds must not only be able to be oxidized by exposed silver halide or by silver halide developer oxidation products, but must also be able to use the coloring compounds themselves to reduce.
• the respective rates of the oxidation or reduction reaction must be optimally adjusted to one another in such a way that the ED compound is already oxidized to a remarkable extent in the course of development before it in turn can reduce the coloring compound.
• the known ED connections do not meet all of these requirements. Regarding what is expressed, for example, in an insufficient color density and / or in an unacceptable color haze of the color transfer images produced.
• ED compounds also results in a high sensitivity to oxidation, which is manifested in premature, non-imagewise consumption of the ED compounds by oxidation and thereby deteriorated image properties of the transfer image, which particularly consist in an insufficient color density, when the photographic recording material is stored for a long time.
• DE-OS 2 809 716 it is also known to use ED compounds not as such, but in the form of a less oxidation-sensitive precursor compound, from which the actual ED compound is only formed under the conditions of alkaline development. Examples of this are the ED connections ED-8, ED-9 and ED-10 of the aforementioned German published application.
• the invention has for its object to provide new oxidation-stable ED precursor compounds that contribute to a good storage stability of the photographic material exhibit elevated temperature and / or humidity and from which ED compounds with a high reduction capacity are only formed under the conditions of alkaline development.
• ED compounds with a high reduction capacity are only formed under the conditions of alkaline development.
• they are intended to enable the generation of color transfer images with improved color density if they are used in combination with non-diffusing, reducible coloring compounds.
• the ED precursor compounds according to the invention are suitable for use in color photographic recording materials wherever it is a question of introducing strong reducing agents into the layers in a capped form, be it as a capped developing agent for silver halide or as a capped reducing agent to prevent the undesired diffusion of oxidation products, resulting from the development of silver halide. It is irrelevant what kind of coloring compounds are used for color image generation. These can be color couplers or coloring compounds that release diffusible dyes as a result of the development (color releasers). However, the preferred use of the ED precursor compounds according to the invention can be seen in the combination with non-diffusing, reducible coloring compounds which, in reduced form, release diffusible dyes under the conditions of alkaline development.
• a preferred object of the invention is therefore a color photographic recording material with at least one light-sensitive silver halide emulsion layer and a combination of a non-diffusing, reducible coloring compound which is capable of releasing a diffusible dye in the reduced state under the alkaline development conditions, and a non-diffusing electron donor precursor compound (ED precursor compound), from which a non-diffusing electron donor compound (ED compound) is formed under the alkaline development conditions, which is able to reduce the non-diffusing coloring compound under the alkaline development conditions, characterized in that the recording material is a compound of the ED precursor compound contains general formula I.
• the aromatic group represented by R 1 in formula I can be a carbocyclic group, for example a phenyl, naphthyl or anthracenyl group or a 5- or 6-membered heterocyclic group with at least one of the heteroatoms N, 0, S as a ring member, for example one Furyl, thienyl, pyrryl or pyridyl group.
• the carbocyclic and heterocyclic aromatic groups can be unsubstituted or mono- or polysubstituted and contain fused carbocyclic or heterocyclic rings, which in this case need not be aromatic.
• the aryl group represented by R 2 in formula I is in particular a phenyl group, which can also be mono- or polysubstituted.
• the acyl group represented by R 2 in formula I is derived from aliphatic or aromatic carboxylic acids of the formula R-COOH, in which R represents alkyl, alkenyl, aryl or a heterocyclic group, or is, for example, a carbamoyl radical.
• Suitable substituents on the aromatic groups represented by R and on the aryl group represented by R are: halogen such as fluorine, chlorine, bromine or iodine, hydroxy, sulfo, sulfamoyl, trifluoromethyl, trifluoromethylsulfonyl, amino, nitro, cyano, carboxy, carbamoyl , Alkoxycarbonyl, alkyl, alkenyl, cycloalkyl, in particular cyclohexyl or cyclopentyl, aryl, in particular phenyl, or heterocyclic groups, where the last-mentioned groups (alkyl, alkenyl, cycloalkyl, aryl and heterocyclic groups) can contain further substituents, for example those of the aforementioned Type and wherein said alkyl, alkenyl, cycloalkyl, aryl or heterocyclic groups ent-.
• halogen such as fluorine, chlorine, bromine
• the alkyl or alkenyl groups represented by R 2 or present as substituents in R and R can be straight or branched and contain 1-22 C atoms, and can also be further substituted, for example by halogen (such as fluorine, chlorine or bromine), hydroxy , Amino, alkoxy, aroxy, alkylthio, arylthio, a heterocyclic thioether group, alkylsulfonyl, arylsulfonyl or a heterocyclic group, such as a 5- or 6-membered heterocyclic ring linked via a ring nitrogen atom.
• halogen such as fluorine, chlorine or bromine
• R 1 is an optionally substituted phenyl group and R 2 is, in preferred embodiments, an alkyl radical having 1 to 3 C atoms, which may optionally be substituted by halogen, alkoxy, aroxy or hydroxyl.
• all of the substituents present in the ED precursor compound are such that the ED precursor compound cannot be diffusively incorporated into photographic layers.
• at least one of the substituents present for example at least one of the radicals R 1 and R, contains a ballast radical.
• the radical R 1 is preferably such that even after the acyl radical -COR 2 has been split off under the influence of alkali, the residual molecule remains diffusion-resistant or has only a limited diffusibility.
• a diffusion-resistant incorporation of the ED precursor compound is particularly desirable because these compounds have an exact localization in a specific layer or be used in a certain quantity relation to assigned non-diffusing, reducible coloring compounds, which should not change significantly even if the photographic recording material is stored for a long time.
• ballast residues Such residues are to be regarded as ballast residues, which make it possible to incorporate the compounds according to the invention in a diffusion-resistant manner in the hydrophilic colloids usually used in photographic materials.
• Organic radicals which generally contain straight-chain or branched aliphatic groups with generally 8 to 22 C atoms and optionally also carbocyclic or heterocyclic aromatic groups are preferably suitable for this purpose. With the remaining part of the molecule, these residues are either direct or indirect, for example. connected via one of the following groups; -NHCO-, -NHS0 2 - ' -NR-, where R is hydrogen or alkyl, -O- or -S-.
• the diffusion-proofing radical can also contain water-solubilizing groups, such as sulfo groups or carboxyl groups, which in certain cases can also be present in anionic form. Since the diffusion properties depend on the molecular size of the total compound used, it is sufficient as ballast residues in certain cases, for example if the total molecule used is large enough or if the ED precursor compounds are incorporated into the layers using so-called oil-forming agents or high-boiling coupler solvents in emulsified form shorter chain residues, for example isoamyl or tert-butyl residues, can also be used.
• water-solubilizing groups such as sulfo groups or carboxyl groups, which in certain cases can also be present in anionic form. Since the diffusion properties depend on the molecular size of the total compound used, it is sufficient as ballast residues in certain cases, for example if the total molecule used is large enough or if the ED precursor compounds are incorporated into the layers using so-called oil-forming agents or high
• the non-diffusing ED precursor compounds used according to the invention are listed below:
• the ED compounds according to the invention are ⁇ -substituted malonic acid diamides.
• aromatic amines of the formula R 1 -NH 2 which are condensed with diethyl malonate with the liberation of ethanol.
• the ⁇ -bromo compound is prepared from the malonic acid diamide obtained by known methods.
• the bromine atom is then exchanged for the rest -OC O - R 2 .
• the production process is explained below using the example of compound 2.
• the ED precursor compounds according to the invention are the known ED compounds, e.g. Ascorbyl palmitate, as well as the known ED precursor compounds, are superior in that they can be used to produce higher maximum color densities with lower minimum color densities (veils) within a given development time. It remains to be seen whether the higher maximum color densities obtained can be attributed to a slight cleavage (hydrolysis) of the acyl residue and thus to a faster availability of the actual ED compounds or to their higher reducibility or both.
• Another advantage of the ED precursor compounds according to the invention is that they are oxidized insensitive form and are only converted to the actual ED compounds during development by treatment with aqueous alkali (hydrolytic cleavage of the acyl group).
• Alkyl radicals can be straight-chain or branched and generally contain up to 18 carbon atoms. Examples are methyl, n-propyl, tert-butyl, tetradecyl, octadecyl.
• the aryl radicals represented by the radicals R 1 , R 2 and R 3 mentioned are, for example, phenyl groups which can be substituted, for example by long-chain alkoxy groups.
• acylamino radical represented by R 3 the acyl group is derived from aliphatic or aromatic carboxylic or sulfonic acids.
• the fused-on rings completed by R and R 3 are preferably carbocyclic rings, for example fused-on benzene or bicyclo [2,2,1] heptene rings.
• An alkyl radical represented by R 4 can be straight-chain or branched, substituted or unsubstituted and contain up to 21 C atoms. Examples are methyl, nitromethyl, phenylmethyl (benzyl), heptyl, tridecyl; Pentadecyl, heptadecyl, -C 21 H 43 .
• Preferred embodiments of the color releasers used according to the invention are those in which R 1 , R 2 and R 3 together contain in a quinoid carrier radical not more than 8, in particular not more than 5, carbon atoms, and R 4 is an alkyl radical with at least 11 carbon atoms represents.
• R 1 is an alkoxyphenyl radical with at least 12 C atoms in the alkoxy group and R 2 , R 3 , R 4 together contain no more than 8 C atoms.
• the preferably used reducible dye releasers contain, per dye residue A, a diffusion-releasable quinoid carrier residue of the formula wherein R , R 2 , R 3 , R 4 , R have the meanings already given.
• the residues of dyes of all classes of dyes are suitable as dye residues insofar as they are sufficiently diffusible to be able to diffuse through the layers of the light-sensitive material into the image-receiving layer.
• the dye residues can be provided with one or more alkali-solubilizing groups. Suitable alkali-solubilizing groups include carboxyl groups, sulfo groups, sulfonamide groups and aromatic hydroxyl groups. Such alkali-solubilizing groups can already be pre-formed in the dye releasers used according to the invention or only from the cleavage of the dye residue from the carrier residue containing ballast groups sult.
• dyes that are particularly suitable for the novel process, should be mentioned: azo dyes, azomethine, A nthra- chino dyes, phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, including dyes, which complexes with metal ions or complexable.
• the residues of dye precursors are to be understood as the residues of those compounds which, in the course of photographic processing, are subject to customary or additional processing steps, either by oxidation, by coupling, by complex formation or by exposure of an auxochromic group in a chromophoric system, for example by Saponification to be converted into dyes.
• Dye precursors in this sense can be leuco dyes, couplers or dyes that are converted into other dyes during processing. Unless a distinction between dye residues and the residues of dye precursors is of essential importance, the latter are also to be understood below under the term dye residues.
• the color photographic recording material in monochromatic processes contains at least one, in processes for producing multicolored images usually at least three image-forming layer units, each of which has at least one light-sensitive silver halide emulsion layer and one contains the associated combination of a non-diffusing, reducible coloring compound and an electro-donor compound, an ED precursor compound according to the invention being used in at least one layer unit.
• one of the layer units is predominantly sensitive to blue light, another one to green light and a third one to red light, the assigned coloring compounds each providing complement-colored image dyes.
• Assignment and “assigned” is understood to mean that the mutual arrangement of silver halide emulsions, ED compound or ED precursor compound and color releaser is of such a kind that an interaction between them is possible which results in an imaginary correspondence between the formed silver image and allows the consumption of ED compound on the one hand and between the unused ED compound and paint releaser on the other hand, so that an imagewise distribution of diffusible dye is produced in accordance with the non-nickel silver halide.
• light-sensitive silver halide and a combination of color releaser and ED compound need not necessarily be present in the same layer; they can also be accommodated in mutually adjacent layers, each belonging to the same layer unit.
• the reducible color releaser is generally used in a layer in an amount sufficient to produce a color image with the highest possible maxi to produce painterly color density, for example in an amount of 1 - 20 10 -4 mol / m 2.
• the amount of the ED precursor compound according to the invention is matched to that of the paint releasing agent. It should be large enough to achieve the highest possible maximum color density, ie in order to be able to reduce the color splitting as completely as possible. On the other hand, it should not be significantly higher than is necessary for this, so that the resulting reducing agent at the exposed areas can be used as completely as possible through the development of the exposed silver halide.
• the best in a particular case quantity ratios between silver halide, ED-precursor compound and F arbabspalter be determined appropriately based on routine experiments. Useful results can be obtained, for example, if the ED precursor compound is present in each case in a 0.5-5 times molar amount, based on the color releasing agent.
• the suitable quantitative ratio between silver halide and assigned color releaser is approximately in the range of 2 to 20 moles of silver halide per mole of color releaser.
• Separating layers are expediently present between different layer units, which can contain compounds which react with diffusing development products and are able to prevent their diffusion from one layer unit into another. This helps to ensure that the assignment is always limited to one shift unit.
• Such connections are known, for example they are not suitable diffusing hydroquinone derivatives and, for example, the "scavenger compounds” described in the publication "Research Disclosure No. 17 842" (February 1979).
• the ED precursor compounds according to the invention can also perform this function, regardless of the type of coloring compound used (color coupler, color releaser), if the ED precursor compounds according to the invention are incorporated as so-called scavengers in a separating layer between different layer units.
• the interaction between the exposed silver halide and the ED compound is generally accomplished by the oxidized form of the silver halide developer used.
• the latter is oxidized imagewise during development and the oxidation product is in turn able to oxidize the ED compound and thus to avoid the reaction with the color releaser.
• Suitable silver halide developing agents are hydroquinone and its derivatives, pyrocatechol and its derivatives, p-phenylenediamine derivatives and 3-pyrazolidone compounds, in particular 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 4 Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,4-bis- ( hydroxymethyl) -3-pyrazolidone, 1,4-dimethyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, 1- (3-chlorophenyl) -4-methyl-3- pyrazolidone, 1- (4-chlorophenyl) -4-methyl-3-pyrazolidone, 1- (3-chlorophenyl) .- 3-pyrazolidone, 1- (4-chlorophenyl
• a combination of different silver halide developing agents can also be used.
• the silver halide developing agents can be contained in an alkaline developer preparation or also in whole or in part in one or more layers of the color photographic recording material to be processed.
• a light-sensitive element which contains one or more silver halide emulsion layer units and the reducible color releasers and ED compounds or their precursors associated therewith, and an image receiving element in which, by the image transfer, the released ones Dyes the desired color image is generated.
• an image receiving element in which, by the image transfer, the released ones Dyes the desired color image is generated.
• the image-receiving element can accordingly be a component of the color photographic recording material, for example in the form of an image-receiving layer which is arranged below the light-sensitive element on a transparent support, with an opaque, preferably light-reflecting, binder layer advantageously being located between the image-receiving layer and the light-sensitive element.
• the dye mordants are dispersed in the receiving layer in one of the usual hydrophilic binders, e.g. in gelatin, polyvinylpyrrolidone, completely or partially hydrolyzed cellulose esters. Of course, some binders can also act as mordants, e.g.
• Copolymers or polymer mixtures of vinyl alcohol and N-vinylpyrrolidone as described, for example, in DE-AS 1 130 284, and also those which are polymers of nitrogen-containing quaternary bases, e.g. Polymers of N-methyl-2-vinylpyridine, as described, for example, in US Pat. No. 2,484,430.
• Further usable binders are, for example, guanylhydrazone derivatives of alkyl vinyl ketone polymers, as described in US Pat. No. 2,882,156, or guanylhydrazone derivatives of acyl styrene polymers, as described for example in DE-OS 2 009 498.
• the color photographic recording material according to the invention may also contain acidic layers and so-called braking or retarding layers, which together form a so-called integral neutralization system.
• Such an integral neutralization system can be arranged in a known manner between the layer support and the image receiving layer arranged thereon or at another location in the layer structure, e.g. above the photosensitive layers, i.e. beyond these light-sensitive layers, viewed from the image-receiving layer.
• the neutralization system is usually oriented so that the braking or retarding layer is between the acid layer and the point at which an alkaline developing liquid or paste is exposed.
• Such a neutralization system can also contain two or more brake layers in a known manner.
• the mono-sheet material may be composed in such a way here that separate two different components are produced, namely the light-sensitive part (layer elements 1 - 4) and the covering sheet (layer elements 5 - 7), which then auffactge layer side - considered and are connected to each other, optionally using spacer strips so that a space is formed between the two parts for receiving a precisely measured amount of a developer preparation.
• the layer elements 5 and 6, which together form the neutralization system, can also be arranged, albeit in the opposite order, between the layer support and the image-receiving layer of the light-sensitive part.
• Means can also be provided to introduce a developer preparation between the light-sensitive part and the cover sheet, for example in the form of a laterally arranged, splitable container which when subjected to mechanical forces, its contents pour out between two adjacent layers of the mono-sheet material.
• the developer preparation can also contain developer compounds which, however, have to be matched to the type of color-providing compounds.
• Other possible components of the developer preparation are thickeners for increasing the viscosity, for example hydroxyethyl cellulose, silver halide solvents, for example sodium thiosulfate, or one of the bis-sulfonylalkane compounds described in DE-OS 2 126 661, opacifiers for producing opaque layers, for example pigments of TiO 2 , ZnO, barium sulfate, barium stearate or kaolin.
• some of these components can also be embedded in one or more layers of the color photographic recording material according to the invention.
• the imagewise exposed photosensitive element and the image-receiving sheet were impregnated with a treatment solution of the composition given below and pressed together on the layer side:
• the sheets were separated from one another and the image-receiving sheet was washed for 30 seconds. After drying, the Dmin / Dmax values of the positive blue-green image were measured.
• the recording material was exposed through the transparent support behind a conventional gray wedge and in an open dish at 22 ° C. for 2 min. developed with a bath of the following composition:
• Example 5 The procedure was as in Example 5, but instead of the photosensitive element described there, those were used which, as scavengers in layers 2 and 4, were 1.5 g of one of the compounds 2 and 13 according to the invention and 1.5 g of dibutyl phthalate each contained oil formers. Processing was carried out as in Example 5.
• the recording materials obtained according to Examples 5, 6 and 7 provided transfer images of comparable good color separation.
• the compounds according to the invention can also be used particularly advantageously as oxform scavengers in photographic layers because of the significantly lower tendency to fog.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=6145733

Family Applications (1)

Country Status (4)

Cited By (1)

Families Citing this family (1)

Citations (3)

Family Cites Families (1)

• 1981
  • 1981-11-05 DE DE19813144037 patent/DE3144037A1/de not_active Withdrawn
• 1982
  • 1982-10-23 DE DE8282109798T patent/DE3271427D1/de not_active Expired
  • 1982-10-23 EP EP82109798A patent/EP0078959B1/fr not_active Expired
  • 1982-10-25 US US06/436,581 patent/US4420557A/en not_active Expired - Fee Related
  • 1982-11-04 JP JP57192629A patent/JPS5886542A/ja active Pending

Patent Citations (3)

Also Published As

Similar Documents

Legal Events