EP0055858B1 - Photographische Produkte, photographisches Diffusionstransferverfahren und dafür verwendete Verbindungen - Google Patents

Photographische Produkte, photographisches Diffusionstransferverfahren und dafür verwendete Verbindungen Download PDF

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Publication number
EP0055858B1
EP0055858B1 EP19810110833 EP81110833A EP0055858B1 EP 0055858 B1 EP0055858 B1 EP 0055858B1 EP 19810110833 EP19810110833 EP 19810110833 EP 81110833 A EP81110833 A EP 81110833A EP 0055858 B1 EP0055858 B1 EP 0055858B1
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Prior art keywords
compound
processing composition
image
assemblage
layer
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EP19810110833
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English (en)
French (fr)
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EP0055858A2 (de
EP0055858A3 (en
Inventor
Avinash C. Mehta
George H. Nawn
Lloyd D. Taylor
James R. Bartels-Keith
Alan L. Borror
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Polaroid Corp
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Polaroid Corp
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Priority claimed from US06/222,542 external-priority patent/US4355101A/en
Priority claimed from US06/222,543 external-priority patent/US4355092A/en
Priority claimed from US06/222,502 external-priority patent/US4390613A/en
Application filed by Polaroid Corp filed Critical Polaroid Corp
Publication of EP0055858A2 publication Critical patent/EP0055858A2/de
Publication of EP0055858A3 publication Critical patent/EP0055858A3/en
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Publication of EP0055858B1 publication Critical patent/EP0055858B1/de
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    • 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

Definitions

  • This invention relates to a photographic assemblage, a diffusion transfer photographic process and the compounds used therefor.
  • Diffusion transfer photographic assemblages wherein images are formed in colour by the use of image dye-providing materials such as dye developers are well known in the art.
  • multicolour transfer images ae formed by processing an exposed multicolour photosensitive silver halide element with an aqueous alkaline processing composition distributed between two sheet-like elements, one of these elements including an image receiving layer.
  • the processing composition is so applied and confined within and between the two sheet-like elements as not to contact or wet outer surfaces of the two superposed elements, thus providing a film unit whose external surfaces are dry.
  • the processing composition preferably is distributed in viscous form from a pressure rupturable container.
  • US ⁇ A ⁇ 3,260,597 discloses that mercaptoazole development restrainers or "arrestors", such as 1-phenyl-5-mercaptoazole, can not be used in the aqueous alkaline processing composition in any appreciable amount because development of exposed silver halide will be stopped prematurely particularly in the outer blue and green sensitive emulsion layers of a multicolour system.
  • blocked development restrainers which are designed to provide a timed release of a development restrainer during the development process. See, for example, US-A-3,698,898 which discloses the use of quinone- or napthoquinone-methide precursors which release a photographic reagent such as 1-phenyl-5-mercaptotetrazole in the presence of alkali; US-A-4,009,029 which discloses a class of cyanoethyl-containing blocked development restrainers; DE-A-2,427,183 which discloses various blocked development restrainers, and US-A-3,260,597 and 3,265,498, referred to above, which discloses hydrolyzable blocked restrainers.
  • Yet another object is to provide a diffusion transfer photographic process wherein the pH of the processing composition initially is substantially equal to or greater than the pKa of the substituent on the phenyl ring of the phenylmercaptoazole compound and subsequently, during development, the pH is lowered below the pKa.
  • Still another object is to provide a diffusion transfer photographic assemblage wherein the substituted phenylmercaptoazole compounds may be incorporated in the aqueous alkaline processing composition.
  • a further object is to provide a diffusion transfer photographic assemblage wherein the substituted phenylmercaptotetrazole compounds may be incorporated in the photosensitive element.
  • Yet another object is to provide a diffusion transfer photographic assemblage wherein the photographic speed of one or more silver halide emulsions may be increased.
  • a still further object is to provide a diffusion transfer photographic assemblage wherein fog development may be decreased.
  • Another object is to provide novel colour diffusion transfer photographic assemblages and processes.
  • a diffusion transfer photographic assemblage comprising a photosensitive element comprising a support carrying at least one silver halide emulsion layer having associated therewith an image dye-providing material, a second sheet-like element superposed or superposable upon said photosensitive element, an image receiving layer positioned in one of said elements, means for lowering the pH of an aqueous alkaline processing composition positioned in one of said elements, a rupturable container releasably holding an aqueous alkaline processing composition capable, when distributed between a pair of predetermined layers carried by said photosensitive element and said second element, of developing said silver halide emulsion and providing a diffusion transfer image on said image receiving layer;
  • This assemblage is characterized in that it includes at least one compound represented by the formula wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6- membered heterocyclic moiety, R is H, an alkali metal or a
  • R 1 is ionizable to an anion, preferably about 8.5 or above.
  • the compounds which are useful according to the invention are generally phenylmercaptoazoles wherein the substituted phenyl moiety is attached to either a nitrogen atom or a carbon atom of the azole moiety. Accordingly, the compounds may be represented by either of the following formulas which are both within generic Formula A.
  • the heterocyclic moieties formed by X preferably include those wherein the heterocyclic atoms (i.e., atoms other than carbon) are members of a single heterocyclic ring as contrasted with compounds containing fused or condensed heterocyclic rings in which the heterocyclic atoms are members of more than one heterocyclic ring.
  • suitable compounds include monoazoles such as benzoazoles, benzothiazoles, etc.; diazoles such as benzimidazoles; triazoles such as 1,2,4-triazoles, etc.; tetrazoles and pyrimidines.
  • the compounds include a tetrazole nucleus.
  • Suitable substituents (R i ) on the phenyl moiety include the following typical substituents where Z is H, alkyl having from 1 to 10 carbon atoms, aralkyl such as benzyl or phenethyl, phenyl or substituted phenyl.
  • the invention also relates to novel componds of the formula wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6- membered heterocyclic moiety, R is H, an alkali metal or a group which is cleavable in aqueous alkaline medium and Z is H, alkyl having from 1 to 10 carbon atoms, aralkyl, phenyl or substituted phenyl.
  • the compounds may include a mercaptan group attached to a carbon atom of the azole nucleus or may include a blocking group attached to the sulfur atom with the blocking group designed to cleave from the molecule in an aqueous alkaline medium to provide a timed release of the desired phenylmercaptoazole compound.
  • R is a blocking group it may be any suitable blocking group such as, for example, those which cleave by hydrdolysis; those which cleave by quinone methide elimination such as disclosed in US-A-3,698,898; those which cleave by hydrolysis followed by quinone methide elimination and those which cleave by ß-elimination (e.g.
  • R is CH2-CH2-CN, where R 2 is alkyl, and where R 3 and R 4 are H or alkyl).
  • Typical suitable blocking groups include, for example, and succinimido groups which are substituted on the nitrogen atom with alkyl or aryl as disclosed in US-A-3,888,677.
  • R is ⁇ CH 2 ⁇ CH 2 SO 2 R 5 where R is alkyl, aryl or substituted aryl.
  • Cleavage of the blocking group in aqueous alkaline medium releases, in a timed fashion during development, the substituted phenylmercaptoazole moiety.
  • Cleavage of the blocking group occurs according to the following reaction sequence: ROH or R' where R' is R minus a proton.
  • the rate of release of the substituted phenylmercaptoazole moiety is temperature dependent, that is, more is released as the temperature at which processing of the film unit is effected rises.
  • more of the substituted phenylmercaptoazole moiety is made available at elevated temperatures, i.e., above room temperature, where more is typically desired, less is released at room temperature and even less below room temperature where lesser amounts are needed.
  • these blocked compounds which are utilized according to the invention provide more uniform sensitometry for the film units of the invention over a wide temperature range of processing.
  • the sensitometry of the film units which include such blocked compounds according to the invention is less temperature dependent than would otherwise be the case.
  • the compounds which are useful according to the invention have been found to modify and/or control the sensitometry when present during diffusion transfer processing of an exposed photosensitive element, particularly when such processing is carried out at elevated temperatures, e.g., at about 35°C.
  • modification and/or control include a speed increase for one or more of the silver halide emulsions in a multicolour diffusion transfer photographic system and/or an increase in the D max of one or more of the individual colours due to control of fog development, as will be illustrated in detail below herein.
  • the advantageous results obtained through the use of the mercaptoazole compounds according to the invention are not completely understood. However, to further aid those skilled in the art to understand and practice the invention, the proposed theoretical mechanism by which the advantageous results are thought to be effected will be discussed here.
  • the diffusion transfer photographic system has been proved to be operative and highly effective through extensive experimentation and the proposed theoretical mechanism is not to be construed as being limiting of the invention. It is theorized that the results obtained according to the invention are due to the compounds - performing different functions at different stages of the development process, that is, as weak silver solvents and promoters of development at one stage of the development process and as development inhibitors, or restrainers, at another stage of the development process, and that the dual functions of these compounds within the diffusion transfer photographic system are pH dependent.
  • the processing composition employed in the process has a very high pH, e.g., from about 13-14, and during the development process each layer of the multilayer film unit goes through a broad pH range which includes very high pH levels and relatively low pH levels.
  • the pH is substantially equal to or above the pKa of the substituent R i on the phenyl F ring, the dianion is formed, for example, and acts as a weak silver solvent to form relatively soluble silver salts, thus promoting development.
  • the pH falls below the pKa of the substituent R i , the monoanion is formed, for example, and the silver salt of the monoanion of the compound is very low in solubility resulting in a development restrainer action.
  • the compounds used according to the invention may be incorporated in various locations within the diffusion transfer film unit such as, for example, in the processing composition, in one or more layers within the photosensitive element or in one or more layers in the image-receiving element such as the image-receiving layer.
  • development of the exposed photosensitive element is carried out with a processing composition having an initial pH substantially equal to or above the pKa of R i , at least for some period of time after the processing composition comes into contact with the mercaptoazole compound so as to enable the substituent to ionize to form the dianion.
  • the pH of the environment where the compound is located is reduced below the pKa of R, so as to form the monoanion.
  • the mercaptoazole compounds which are useful according to the invention may be prepared by reactions which are well known in the art.
  • 2-mercaptoimidazoles can be prepared by the reactions disclosed in The Chemistry of Heterocyclic Compounds Vol. 6: Imidazole and Its Derivatives, Part I, Hofmann, Interscience Publishers, Inc., New York, 1953, pages 77-85;
  • mercaptothiazoles and mercaptobenzothiazoles can be prepared according to the methods disclosed in The Chemistry of Heterocyclic Compounds Vol.
  • Mercapto-1,2,4-triazoles can be prepared by known literature techniques as described, for example, in Jour. Chem. Soc. E. Haggarth 1163 (1949).
  • the compounds within Formulas A, B and C where R is a blocking group can be prepared also by known reactions such as by performing the monosodium salt of the appropriate mercaptoazole derivative and carrying out a condensation reaction with the appropriate blocking group in a solvent such as acetone, ethanol, acetonitrile, etc., or by reacting the mercaptoazole derivative with the appropriate blocking group in a suitable solvent in the presence of one equivalent of sodium bicarbonate.
  • R may also be a precursor of a substituent which has the requisite properties and the desired substituent may be formed in situ.
  • R may also be a precursor of a substituent which has the requisite properties and the desired substituent may be formed in situ.
  • R may also be a precursor of a substituent which has the requisite properties and the desired substituent may be formed in situ.
  • Table I lists the pKa of various substituents in certain of the compounds illustrated above.
  • compound II is a weak to moderate silver solvent at high pH while PMT is not. Further, it is evident that when the oxime substituent is protonated it reverts to behaviour which is similar to that of PMT. In fact, compound II forms an even less soluble salt in neutral solution than does PMT, thus giving it greater differentiation on the availability of silver in soluble form as the pH drops in the diffusion transfer development process.
  • the compounds which are employed according to the invention may be incorporated in any location in the assemblage with the preferred location in any particular instance being dependent upon various factors such as the compound itself, the type of assemblage and the results desired.
  • the compounds generally may be incorporated in the assemblage in any useful amount. Routine scoping tests may be used to ascertain the concentration appropriate for any given assemblage and location.
  • the compounds When the compounds are incorporated in the processing composition they are present preferably in an amount of from about 0.02 to about 0.07 % by weight.
  • the compounds When incorporated in a layer in the photosensitive element the compounds are typically present in a ratio of from about 1 mg/m 2 to about 3 mg/m 2 to about 3800 M g/ M 2 of silver.
  • the total amount required per film unit to give a desired result is less than that required when the compound is incorporated in the processing composition. It has also been observed that too great an amount of the compounds can lead to reduced control of one or more of the image dye-providing materials which results in high D mln values in the photographic reproduction or can lead to a loss in Dmax for one or more colours as will be apparent from the Examples.
  • compounds according to the invention can be incorporated in more than one location in the diffusion transfer assemblage.
  • part of the total quantity of the substituted phenylmercaptoazole compound can be incorporated in the processing composition and the remainder in the photosensitive element.
  • the quantity available can be appropriate to provide a speed increase for on or more silver halide emulsions (silver solvent effect) without providing any undesired premature development restraint and the additional quantity dissolved during processing could give a total concentration desired to prevent further development.
  • This embodiment is particularly useful where R is H or an alkali metal for the compound incorporated in the processing composition and R is a cleavable group for the compound incorporated in the photosensitive element.
  • the compounds used in accordance with the invention may be used generally in association with any silver halide emulsion. It is preferred to use the compounds in a diffusion transfer photographic assemblage which includes a negative silver halide emulsion, i.e., one which develops in the areas of exposure.
  • the diffusion transfer photographic assemblage of the invention may include any image dye-providing material in association with the silver halide emulsion(s).
  • the image dye-providing materials which can be utilized generally may be characterized as either (1) initially soluble or diffusible in the processing composition but which are selectively rendered nondiffusible imagewise as a function of development; or (2) initially-insoluble or nondiffusible in the processing composition but which selectively provide a diffusible product imagewise as a function of development.
  • the image dye-providing materials may be complete dyes or dye intermediates, e.g., colour couplers.
  • the requisite differential in mobility or solubility may be obtained, for example, by a chemical reaction such as a redox reaction, a coupling reaction or a cleavage reaction.
  • the image dye-providing materials are dye developers which are initially diffusible materials.
  • the dye developers contain, in the same molecule, both the chromophoric system of a dye and a silver halide developing function as is described in US-A-2,983,606.
  • Other image dye-providing materials which may be used include, for example, initially diffusible coupling dyes such as are useful in the diffusion transfer process described in US-A-3,087,817 and which are rendered nondiffusible by coupling with the oxidation product of a colour developer; initially nondiffusible dyes which release a diffusible dye following oxidation, sometimes referred to as "redox dye releaser" dyes, such as described in US-A-3,725,062 and 4,076,529; initially nondiffusible image dye-providing materials which release a diffusible dye following oxidation and intramolecular ring closure as are described in US-A-3,433,939 or undergo silver assisted cleavage to release a diffusible dye in accordance with the disclosure of US-A-3,719,489;
  • the compounds may be incorporated into the photographic assemblage by any suitable technique.
  • the compounds are incorporated in a separate discrete layer or in a silver halide emulsion layer they are typically coated from a water dispersion and the layer includes a binder material such as gelatin or the like.
  • the diffusion transfer assemblages of the invention include those wherein the image receiving element is designed to be separated from the photosensitive element after processing and integral positive-negative diffusion transfer film assemblage which are retained intact after processing.
  • the diffusion transfer film units of the invention utilize initially diffusible dye developers as the image dye-providing materials.
  • a photosensitive element containing a dye developer and a silver halide emulsion is photoexposed and a processing composition applied thereto, for example, by immersion, coating, spraying, flowing; etc., in the dark.
  • the exposed photosensitive element is superposed prior to, during, or after the processing composition is applied, on a sheet-like support element which may be utilized as an image-receiving element.
  • the processing composition is applied to the exposed photosensitive element in a substantially uniform layer as the photosensitive element is brought into superposed relationship with the image-receiving layer.
  • the processing composition positioned intermediate the photosensitive element and the image-receiving layer, permeates the emulsion to initiate development of the latent image contained therein.
  • the dye developer is immobilized or precipitated in exposed areas as a consequence of the development of the latent image. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation and especially as regards its solubility in alkaline solutions.
  • the dye developer is unreacted and diffusible and thus provides an imagewise distribution of unoxidized dye developer, diffusible in the processing composition, as a function of the point-to-point degree of exposure of the silver halide emulsion. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer of element, said transfer substantially excluding oxidized dye developer.
  • the image-receiving layer receives a depthwise diffusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide a reversed or positive colour image of the developed image.
  • the image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer.
  • the desired positive image is revealed by separating the image-receiving layer from the photosensitive element at the end of a suitable imbibition period.
  • the image-receiving layer need not be separated from its superposed contact with the photosensitive element, subsequent to transfer image formation, if the support for the image-receiving layer, as well as any other layers intermediate said support and image-receiving layer, is transparent and a processing composition containing a substance, e.g., a white pigment, effective to mask the developed silver halide emulsion or emulsions is applied between the image-receiving layer and said silver halide emulsion or emulsions.
  • a substance e.g., a white pigment
  • Dye developers are compounds which contain, in the same molecule, both the chromophoric system of a dye and also a silver halide developing function.
  • a silver halide developing function is meant a grouping adapted to develop exposed silver halide.
  • a preferred silver halide development function is a hydroquinonyl group.
  • the development function includes a benzonoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidised.
  • Multicolour images may be obtained using dye developers in diffusion transfer processes by several techniques.
  • One such technique contemplates obtaining multicolour transfer images utilizing dye developers by employment of an integral multilayer photosensitive element, such as is disclosed in the aforementioned US ⁇ A ⁇ 2,983,606 and in US-A-3,345,163, wherein at least two selectively sensitized photosensitive strata, superposed on a single support, are processed, simultaneously and without separation, with a single common image-receiving layer.
  • a suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer said emulsions having associated therewith, respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • the dye developer may be utilized in the silver halide emulsion layer for example in the form of particles, or it may be disposed in a layer behind the appropriate silver halide emulsion layer.
  • Each set of silver halide emulsion and associated dye developer layers may be separated from other sets by suitable interlayers, for example, by a layer or stratum of gelatin or polyvinyl alcohol.
  • a yellow filter in front of the green-sensitive emulsion and such yellow filter may be incorporated in an interlayer.
  • a yellow dye developer of the appropriate spectral characteristics and present in a state capable of functioning as a yellow filter may be so employed and a separate yellow filter omitted.
  • US ⁇ A ⁇ 3,647,437 is concerned with improvements in products and processes disclosed in said US ⁇ A ⁇ 3,415,644, and discloses the provision of light-absorbing materials to permit such processes to be performed, outside of the camera in which photoexposure is effected, under much more intense ambient light conditions.
  • a light-absorbing material or reagent preferably a pH-sensitive phthalein dye, is provided so positioned and/or constituted as not to interfere with photoexposure but so positioned between the photoexposed silver halide emulsions and the transparent support during processing after photoexposure as to absorb light which otherwise might fog the photoexposed emulsions.
  • the light-absorbing material is so positioned and/or constituted after processing as not to interfere with viewing the desired image shortly after said image has been formed.
  • the light-absorbing material also sometimes referred to as an optical filter agent
  • a light-reflecting material e.g., titanium dioxide.
  • concentration of the light-absorbing dye is selected to provide the light transmission opacity required to perform the particular process under the selected light conditions.
  • the light-absorbing dye is highly coloured at the pH of the processing composition, e.g., 13-14, but is substantially non-absorbing of visible light at a lower pH, e.g., less than 10-12.
  • This pH reduction may be effected by an acid-reacting reagent appropriately positioned in the film unit, e.g., in a layer between the transparent support and the image-receiving layer.
  • the dye developers are preferably selected for their ability to provide colors that are useful in carrying out substractive colour photography, that is, the previously mentioned cyan, magenta and yellow.
  • the dye developers employed may be incorporated in the respective silver halide emulsion or, in the preferred embodiment, in a separate layer behind the respective silver halide emulsion, and such a layer of dye developer may be applied by use of a coating solution containing the respective dye developer distributed, in a concentration calculated to give the desired coverage of dye developer per unit area, in a film-forming natural, or synthetic, polymer, for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the processing composition.
  • a particularly useful film unit according to the invention is one wherein the photosensitive element includes a light-reflecting layer between the silver halide layer and the image dye-providing layer (as described in CDN-A-668,952), the substrate of the photosensitive element carries the polymeric acid neutralizing layer which in turn carries the timing layer (as described in US-A-3,573,043) and the processing composition includes an oximated polydiacetone acrylamide thickening agent (as described in US-A-4,202,694).
  • the photosensitive element comprised a subcoated transparent polyethylene terephthalate photographic film base having coated thereon the following layers in succession:
  • the image-receiving element comprised a transparent polyethylene terephthalate film base coated with the following layers in succession:
  • the film unit was processed with an aqueous alkaline processing composition as follows:
  • a film unit according to the invention was prepared identical to the control with the exception that the processing composition further included 0.05% of compound II.
  • the film units were processed at room temperature as follows: one half of each film unit was exposed through the transparent base of the image-receiving element to light from a Xenon source (100 meter candle-seconds) which was passed in turn through an ultraviolet filter, neutral density filters to reduce the film plane light flux to 0.5 mcs, and a Wratten 47B blue filter; the other half of each film unit was not exposed.
  • the film units were then processed by passing them through a pair of rollers at a gap spacing of about 0.08 mm and the relative amount of silver developed (a function of the infra-red light absorbed) was measured as a function of time for both the exposed and unexposed areas. The relative amount of developed silver vs time curves are shown in Fig. 1.
  • the photosensitive element comprised a subcoated opaque polyethylene terephthalate photographic film base having coated thereon the following layers in succession:
  • the image-receiving element was identical to that described in Example I.
  • the film unit was processed with a control aqueous alkaline processing composition which was the same as the control described in Example I with the exception that it included 0.55 g of benzotriazole and did not include any 4-amino-pyrazolo (3,4-d)pyrimidine.
  • the film unit was exposed (0.5 meter-candle-seconds) on a sensitometer to a photographic test exposure scale, or step wedge, through the transparent support of the image-receiving element and processed at 24°C with the processing composition by passing the film unit through a pair of pressure rollers set at a gap spacing of about 0.08 mm.
  • the film unit was retained intact and viewed through the transparent base. There was obtained a well developed image.
  • the neutral density column of the image was read on the densitometer to obtain the D max values for red, green and blue curves, respectively.
  • the speed of the red, green and blue curves, respectively (defined as the negative log of the relative exposure required to give red, green and blue absorption in the neutral column a reflection density of 0.75) was measured. The values obtained are shown in Table IV.
  • Example II The experiment described in Example II was repeated with six film units (IIIA-IIIF) which included compound II in the amounts shown in Table V. In addition, certain of the film units were also processed at 35°C. The room temperature data for the control film unit of Example II were used for comparison. In addition, a control film unit was processed at 35°C.
  • a control film unit was prepared as follows:
  • the photosensitive element comprised a subcoated opaque polyethylene terephthalate photographic film base having coated thereon in succession:
  • the image-receiving element comprised a transparent subcoated polyethylene terephthalate film base on which the following layers were coated in succession:
  • the film unit was processed with the processing composition described in Example I as a control with the exception that it included 0.55 g of benzotriazole and 0.93 g of the aqueous colloidal silica dispersion.
  • This experiment represents a comparison of compounds I and II and phenylmercaptotetrazole (PMT) with a control at room temperature.
  • control film unit comprised a subcoated opaque film base having the following layers coated thereon in succession:
  • the image-receiving element comprised a transparent base having coated thereon in succession:
  • control film unit was processed with a processing composition as described in Example V.
  • VIA-VIC Three additional film units (VIA-VIC) were prepared and processed in the same manner with the exception that the processing composition further included 0.05% of PMT, compound I and compound II respectively. The results are shown in Table VIII.
  • the photosensitive element comprised a subcoated transparent polyethylene terephthalate photographic film base having coated thereon the following layers in succession:
  • the image-receiving element was identical to that described in Example V.
  • the film unit was processed with a processing composition as described in Example V.
  • Film Units VIIA-VIIC further included 1 mg/m 2 , 2 mg/ m 2 and 3 mg/m 2 , respectively, of compound II in layer 5 of the photosensitive element and Film Units VIID-VIIF further included 1 mg/m 2 , 2 mg/m 2 and 3 mg/m 2 of compound XI in layer 5 of the photosensitive element.
  • An identical set of film units was also processed 35°C. The results are shown in Table IX.
  • a catalyst was prepared by stirring a mixture of Celite® (10 g) (diatomaceous earth available from Johns Manville) and potassium fluoride dihydrate (15 g) in 250 ml of distilled water for 30 minutes. The water was removed on a rotary evaporator and the solids dried overnight at room temperature under high vacuum. The catalyst was further dried in a vacuum oven at 58-60°C for about two days.
  • a catalyst was prepared by stirring a mixture of 10 g of Celite O (diatomaceous earth available from Johns Manville) and 15 g of potassium fluoride in 250 ml of distilled water for about 30 minutes, removing the water on a rotary evaporator at'56°C and drying the solid under vacuum at 58°-60°C to calculated weight, 196 g.
  • the catalyst (1 g) was added to a stirred solution of 5 g of compound I and 1.8 g of methyl vinyl ketone in 50 ml of dry tetrahydrofuran, and the suspension was stirred under nitrogen at room temperature for three days.
  • the oily residue was taken up in 100 ml of ethyl acetate, washed with 80 ml of saturated sodium bicarbonate and twice with 80 ml of water, dried over sodium sulfate and activated charcoal and the mixture vacuum filtered through diatomaceous earth to give a light yellow solution.
  • the solvent was stripped from the solution by rotary evaporation to give 12.5 g of a light yellow oil.
  • the oil was taken up in a mixture of 20 ml of ethyl acetate and 80 ml of hexane and the solution allowed to stand in a refrigerator overnight.
  • the solvent was stripped by rotary evaporation to give an oily residue which was taken up in 100 ml of hexane and allowed to stand.
  • the negative element comprised an opaque subcoated polyethylene terephthalate film base on which the following layers were coated in succession.
  • the image-receiving element comprised a transparent subcoated polyethylene terephthalate film base upon which there was coated an image-receiving layer coated at a coverage of about 3229 mg/m 2 of: (a) 3 parts of a mixture of 2 parts polyvinyl alcohol and 1 part poly-4-vinylpyridine and (b) 1 part of a graft copolymer comprised of 4-vinylpyridine (4VP) and vinyl benzyl trimethyl ammonium chloride (TMQ) grafted onto hydroxyethyl cellulose (HEC) at a ratio HEC/4VP/TMQ of 2.2/2.2/1; and about 53.8 mg/m 2 of 1,4-butanediol diglycidyl ether.
  • 4VP 4-vinylpyridine
  • TMQ vinyl benzyl trimethyl ammonium chloride
  • the film unit was processed with a processing composition made up as follows:
  • the negative element was exposed (2 meter-candle-seconds) on a sensitometer to a test exposure scale with white light, and then brought together with the image-receiving element and processed at room temperature (24°C) by passing the film unit through a pair of rollers set at a gap spacing of about 0.066 mm.
  • the film unit was kept intact and viewed through the base of the image-receiving element.
  • VIIIA-VIIIG Seven additional film units according to the invention (VIIIA-VIIIG) were prepared. These were identical to the control with the exception that the negatives also included a topcoat layer comprising about 215 mg/m 2 of a blocked compound according to the invention (as shown in Table X) and about 215 mg/m 2 of gelatin.
  • the film units were processed as described above at 24°C and at 35°C. The results are shown in Table X.

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Claims (21)

1. Photographischer Aufbau (Anordnung) zur Erzeugung eines photographischen Diffusions- übertragungsbildes, enthaltend ein lichtempfindliches Element mit einer Unterlage, die mindestens eine Silberhalogenid-Emulsionsschicht trägt, der ein bildfarbstofflieferndes Material zugeordnet ist; ein zweites, folienartiges Element, das auf dem lichtempfindlichen Element liegt oder darüber gelegt werden kann; eine Bildempfangsschicht, die in einem dieser Elemente angeordnet ist; Mittel zur Erniedrigung des pH-Wertes einer wäßrig-alkalischen Entwickiermasse, die in einem dieser Elemente angeordnet sind; einen aufreißbaren Behälter, der freisetzbar eine wäßrig-alkalische Entwicklermasse enthält, die, wenn sie zwischen einem Paar vorbestimmter Schichten, die durch das lichtempfindliche Element und das zweite Element getragen werden, verteilt wird, in der Lage ist, die Silberhalogenid-Emulsion zu entwickeln und auf der Bildempfangsschicht ein Diffusionsübertragungsbild zu erzeugen, dadurch gekennzeichnet, daß der Aufbau mindestens eine Verbindung der Formel
Figure imgb0061
enthält, worin X die nichtmetallischen Atome, die zur Bildung eines Kerns, der eine 5- oder 6-gliedrige heterocyclische Gruppe vervollständigt, notwendig sind, darstellt; R ist H, ein alkalimetall oder eine Gruppe, die in der wäßrig-alkalischen Entwicklermasse aufspaltbar ist; und R1 ist entweder eine Gruppe, die einen pKa-Wert von 7 bis 14 hat und die zu einem Anion ionisierbar ist, wodurch das Silbersalz des durch die Aufspaltung oder Ionisierung von -SR resultierenden Mercaptans in dem pH-Bereich, in welchem R, zu einem Anion ionisiert wird, in der wäßrig-alkalischen Entwicklermasse löslicher gemacht wird als es unterhalb dieses pH-Wertes ist; oder eine Vorstufe einer derartigen Gruppe, worin die Entwicklermasse ursprünglich einen pH-Wert hat, der im wesentlichen gleich oder über dem pKa-Wert von R1 liegt, und wobei die Mittel zur Herabsetzung des pH-Wertes einer wäßrig-alkalischen Entwicklermasse in der Lage sind, den pH-Wert der wäßrig-alkalischen Entwicklermasse auf einen Wert unterhalb des pKa-Wertes von R1 herabzusetzen.
2. Aufbau nach Anspruch 1, worin das lichtempfindliche Element eine Unterlage aufweist, die eine rotempfindliche silberhalogenid-Emulsionsschicht, der ein blaugrünes bildfarbstofflieferndes Material zugeordnet ist, eine grünempfindliche Silberhalogenid-Emulsionsschicht, der ein purpurnes bildfarbstofflieferndes Material zugeordnet ist, und eine blauempfindliche Silberhalogenid-Emulsionsschicht, der ein gelbes bildfarbstofflieferndes Material zugeordnet ist, trägt.
3. Aufbau nach einem der vorhergehenden Ansprüche, worin das (die) bildfarbstoffliefernde(n) Material(ien) (einen) Entwicklerfarbstoff(e) und die Emulsion(en) (eine) negativ arbeitende Emulsion(en) darstellt(darstellen).
4. Aufbau nach einem der vorhergehenden Ansprüche, worin sich die genannte Verbindung in der Entwicklermasse befindet.
5. Aufbau nach Anspruch 4, worin die Verbindung in einer Menge von 0,02 bis 0,07 Gew.-%, bezogen auf die Entwicklermasse, vorhanden ist. -
6. Aufbau nach einem der vorhergehenden Ansprüche, worin das zweite Element eine durchsichtige Unterlage sowie die Mittel zur Erniedrigung des pH-Wertes einer wäßrig-alkalischen Entwicklermasse enthält, und worin die Entwicklermasse Mittel zur Erzeugung einer Schicht aus lichtreflektierendem Pigment zwischen der Bildempfangsschicht und der (den) Silberhalogenid-Emulsionsschicht(en) enthält.
7. Aufbau nach Anspruch 6, worin das lichtreflektierende Pigment Titandioxid darstellt.
8. Aufbau nach einem der vorhergehenden Ansprüche, worin R=H darstellt.
9. Aufbau nach einem der vorhergehenden Ansprüche, worin R, aus
Figure imgb0062
ausgewählt ist.
10. Aufbau nach einem der Ansprüche 1 bis 7 oder 9, worin R eine Gruppe darstellt, die in der wäßrig-alkalischen Entwicklermasse abspaltbar ist und die Verbindung sich im lichtempfindlichen Element befindet.
11. Aufbau nach Anspruch 10, worin R = ―CH2CH2SO2R5 bedeutet, worin R5 eine Alkyl-, Aryl- oder substituierte Arylgruppe darstellt.
12. Aufbau nach einem der vorhergehenden Ansprüche, worin die Verbindung durch die Formeln
Figure imgb0063
dargestellt ist.
13. Aufbau nach einem der Ansprüche 1 bis 11, worin die Verbindung durch die Formel
Figure imgb0064
dargestellt ist.
14. Aufbau nach Anspruch 13, worin R = H oder―CH2―CH2SO2R5 bedeutet, worin R5 eine Alkyl-, Aryl-oder substituierte Arylgruppe darstellt und R1 aus den Gruppen
Figure imgb0065
ausgewählt ist.
15. Aufbau nach einem der Ansprüche 1 bis 7, worin sich die Verbindung in der Entwicklermasse und in dem lichtempfindlichen Element befindet, wobei R = H bedeutet, wenn sich die Verbindung in der Entwicklermasse befindet, und R eine Gruppe bedeutet, die in der wäßrig-alkalischen Entwicklermasse abspaltbar ist, wenn sich die Verbindung im lichtempfindlichen Element befindet.
16. Photographisches Diffusionsübertragungsverfahren unter Verwendung des photographischen Aufbaus nach einem der Ansprüche 1 bis 15, welches die folgenden Schritte umfaßt: Belichtung des lichtempfindlichen Elements mit aktinischer Strahlung; Aufbringen der wäßrig-alkalischen Entwicklermasse auf das belichtete lichtempfindliche Element zwecks Entwicklung und Ausbildung einer bildmäßigen Verteilung von bildfarbstofflieferndem Material als Funktion der Entwicklung und Übertragung mindestens eines Teils der bildmäßigen Verteilung des bildfarbstoffliefernden Materials auf eine Bildempfangsschicht, welche auf dem lichtempfindlichen Element liegt, um auf diese ein Diffusionsübertragungsbild zu erzeugen.
17. Verbindung der Formel
Figure imgb0066
worin X die nichtmetallischen Atome, die zur Bildung eines Kerns, der eine 5- oder 6-gliedrige heterocyclische Gruppe vervollständigt, notwendig sind, darstellt; R ist H, ein Alkalimetall oder eine Gruppe, die in dem wäßrig-alkalischen Medium aufspaltbar ist und Z = H, eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, eine Aralkyl-, Phenyl- oder substituierte Phenylgruppe darstellt.
18. Verbindung nach Anspruch 17, worin die heterocyclische Gruppe aus den Monoazolen (einschließlich der Benzoxazole und Benzothiazole); Diazolen (einschließlich der Benzimidazole); Triazolen; Tetrazolen; und Pyrimidinen ausgewählt ist.
19. Verbindung nach Anspruch 17 oder 18, worin X die nichtmetallischen Atome bedeutet, die zur Vervollständigung der Tetrazolgruppe notwendig sind.
20. Verbindung nach einem der Ansprüche 17 bis 19, worin Z eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen darstellt.
21. Verbindung nach einem der Ansprüche 17 bis 20, worin R =―CH2―CH2―SO2―R5 bedeutet, worin R5 eine Alkyl- oder Arylgruppe darstellt.
EP19810110833 1981-01-05 1981-12-29 Photographische Produkte, photographisches Diffusionstransferverfahren und dafür verwendete Verbindungen Expired EP0055858B1 (de)

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US06/222,543 US4355092A (en) 1981-01-05 1981-01-05 Novel phenylmercaptoazole compounds
US06/222,502 US4390613A (en) 1981-01-05 1981-01-05 Diffusion transfer photographic system utilizing substituted phenylmercaptoazoles
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Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA665952A (en) 1963-07-02 N. Phillips Leslie Polyurethane resinous materials
NL105919C (de) 1956-02-13 1900-01-01
US3087817A (en) 1956-10-03 1963-04-30 Polaroid Corp Process and product for forming color images from complete dyes
US2983606A (en) 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
NL268155A (de) 1960-08-22
US3260597A (en) 1960-12-02 1966-07-12 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers and development arrestors
US3227550A (en) 1962-09-07 1966-01-04 Eastman Kodak Co Photographic color reproduction process and element
GB1119799A (en) * 1964-09-01 1968-07-10 Eastman Kodak Co Substituted mercapto-tetrazoles and their use in photographic processing methods
US3295976A (en) 1964-09-01 1967-01-03 Eastman Kodak Co Novel inhibitors for use in the black and white development of color reversal film
US3433939A (en) 1965-10-22 1969-03-18 Kenneth A Sieloff Decorative night light
US3415644A (en) 1967-03-10 1968-12-10 Polaroid Corp Novel photographic products and processes
US3573043A (en) 1967-03-10 1971-03-30 Polaroid Corp Photographic diffusion transfer color process and composite film unit for use therein
US3594165A (en) 1968-05-13 1971-07-20 Polaroid Corp Novel photographic products and processes
AU421758B2 (en) * 1968-05-24 1972-02-24 International Polaroid Corporation Development process in diffusion transfer photographic systems
US3698898A (en) 1970-12-17 1972-10-17 Polaroid Corp Photographic products and processes employing a compound which in the presence of alkali releases a diffusible photographic reagent
US3647437A (en) 1970-12-18 1972-03-07 Polaroid Corp Photographic products, processes and compositions
US3719489A (en) 1971-06-21 1973-03-06 Polaroid Corp Novel photographic processes and products
US3725062A (en) 1971-07-06 1973-04-03 Eastman Kodak Co Color diffusion processes utilizing hydroquinones which provide dye image materials upon oxidation in alkaline conditions
US4076529A (en) 1972-08-22 1978-02-28 Eastman Kodak Company Photographic diffusion transfer films, processes and compositions with color moiety releasing compound
GB1402819A (en) 1972-10-13 1975-08-13 Du Pont Thio-substituted succinimides and their use in light sensitive photographic material
JPS5119987B2 (de) * 1973-02-05 1976-06-22
US4009029A (en) * 1973-06-05 1977-02-22 Eastman Kodak Company Cyanoethyl-containing blocked development restrainers
CA1020795A (en) 1973-06-05 1977-11-15 Howell A. Hammond Blocked development restrainers
JPS513231A (en) * 1974-06-26 1976-01-12 Fuji Photo Film Co Ltd Karaakakusantenshahoshashinzairyo
DE2529488A1 (de) * 1975-07-02 1977-01-27 Agfa Gevaert Ag Photographisches material fuer das farbstoffdiffusionsuebertragungsverfahren
US4190666A (en) * 1975-08-11 1980-02-26 E. I. Du Pont De Nemours And Company Anti-inflammatory 4,5-diarly-2-(substituted-thio)imidazoles and their corresponding sulfoxides and sulfones
DE2552505C3 (de) * 1975-11-22 1978-12-21 Agfa-Gevaert Ag, 5090 Leverkusen Farbphotographisches Entwicklungsverfahren und farbphotographisches Aufzeichnungsmaterial

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