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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
• • 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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
• • 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
  • Y10S430/158—Development inhibitor releaser, DIR

Definitions

• PHOTOGRAPHIC PRQCESSES This invention relates to novel photographic processes, and more particularly to novel photographic processes which result in the good reproduction of both fine line and continuous tone images.
• Photographic processes are known, such as those utilizing commercially available microfilm, which produce the high contrast required for recordingfine line copy. Such films have a relatively short latitude, and record continuous tone images poorly. It therefore appears highly desirable to provide novel photographic processes which record fine line copy satisfactorily and at the same time produce acceptable continuous tone images. Such processes should result in very high contrast for printed material or small image areas (i.e., high microcontrast or microgamma) and low contrast for large or continuous tone image areas (i.e., low macrogamma or macrocontrast).
• the images provided by such processes should preferably be composed predominantly of silver to provide a permanent record. Images composed primarily of dye are not suitable for certain purposes, such as when the images are to be stored for an extended period of time.
• One object of this invention is to provide novel photographic processes.
• Another object of this invention is to provide novel photographic processes which yield high-contrast images of fine line copy.
• a further object of this invention is to provide novel photographic processes which produce good continuous tone images.
• Another object of this invention is to provide novel photographic processes which result in images which exhibit good edge effects.
• Still another object of this invention is to provide photographic processes-which result in images that exhibit high microcontrast and low macrocontrast.
• an improvement in the method of developing, with primary aromatic color developing agent, an imagewise exposed photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a development inhibitor releasing coupler.
• the improvement comprises conducting development in the presence of a competing coupler which produces substantially no permanent dye in the emulsion layer.
• the photographic silver halide emulsion layer comprises fine silver halide grains, and the development is conducted in the presence of a silver halide solvent.
• the processes of the invention employ a competing coupler which produce substantially no permanent dye in the emulsion layer.
• the coupler may be one which, on reaction with oxidized color developing agent, forms no dye (a leuco dye) or forms a dye that is removed from the coating upon washing in aqueous processing solution.
• the competing coupler utilized is preferably one which forms a diffusible dye on reaction with oxidized aromatic primary amino color developing agent. The dye formed is diffusible and washes out of the layer. Competing couplers of this type are described and referred to in Weller et al. U.S. Pat. No. 2,689,793, issued Sept. 21, 1954, and Salminen U.S. Pat. No. 2,742,832, issued Feb. 17, 1955, the disclosures of which are incorporated herein by reference.
• development inhibitor-releasing coupler is used herein as a word of art to refer to those photographic couplers which, upon reaction with oxidized primary aromatic amine color developing agent, form dye and release a compound which inhibits development.
• the development inhibitorrcleasing couplers which are utilized in the-practice of this invention can embody any photographic coupler radical.
• Typical useful photographic coupler radicals include the 5- pyrazolone coupler radicals, the phenolic (including anaphthol) coupler radicals, and the open-chain ketomethylene coupler radicals.
• 5- pyrazolone coupler radicals are customarily utilized for the formation of magenta dyes; phenolic coupler radicals are generally utilized for the formation of cyan color dyes; and, open-chain ketomethylene coupler radicals are generally utilized in the formation of yellow dyes.
• the coupling position of such coupler radicals is also well known in the art.
• the 5- pyrazolone coupler radicals couple at the carbon atom in the 4-position thereof; the phenolic coupler radicals couple at the carbon atom in the 4-position (relative to the hydroxyl group); and, the open-chain ketomethylene coupler radicals couple at the carbon atom forming the methylene moiety (e.g.
• DIR Development inhibitor-releasing (DIR) couplers which can be utilized herein can be represented by the general formula:
• Cp represents a photographic coupler radical, preferably an open-chain ketomethylene, S-pyrazolone or phenolic (including alpha-naphtholic) coupler radicals, having said 2 substituted in the coupling position of the coupler radical, Z representing an organic group which does not contain a chromophore, does not couple with oxidized primary aromatic amine colordeveloper to form dye, does not inhibit development while attached to Cp, but is released from Cp, on reaction with oxidized primary aromatic amine color developing agent, and either is or forms a compound which inhibits development.
• a photographic coupler radical preferably an open-chain ketomethylene, S-pyrazolone or phenolic (including alpha-naphtholic) coupler radicals, having said 2 substituted in the coupling position of the coupler radical
• Z representing an organic group which does not contain a chromophore, does not couple with oxidized primary aromatic amine colordeveloper to form dye, does not inhibit development while attached to Cp, but is released
• R can be any substituents of the type used in open-chain DIR ketomethylene couplers.
• R can be any substituents of the type used in open-chain DIR ketomethylene couplers.
• R can be any substituents of the type used in open-chain DIR ketomethylene couplers.
• R can be any substituents of the type used in open-chain DIR ketomethylene couplers.
• R can be any substituents of the type used in open-chain DIR ketomethylene couplers.
• Y represents a group which, when released from the coupler on reaction with primary aromatic amine color developing agent, either is or forms a compound which inhibits development.
• Y can represent:
• 2a monothio group such as ortho-nitro or ortho-amino substituted arylmonothio groups (such as, 2-nitrophenyl and Z-aminophenyl), a carbon containing heterocyclic monothio group (generally having a five to six membered ring containing at least one heteronitrogen, oxygen or sulfur atom and preferably one to four heteronitrogen atoms) including heterocyclic radicals, such as, tetrazolyls, triazinyls, triazolyls, oxazolyls, oxadiazolyls, diazolyls, thiazyls, thiadiazolyls, benzoxazolyls, benzothiazolyls, pyrimidyls, pyridinyl, quinolinyls, etc., and in which the aryl-,'heterocyclic-- moieties of the monothio group are either unsubstituted or substituted with various groups, such as
• 2-benzothiazolylthio 1-phenyl-5-tetrazolylthio, l- (4-carbo-methoxyphenyl) S-tetrazolylthio, S-phenyll,3,4-oxadiazolyl-2thio, 2-phenyl-5- l ,3 ,4 )-ox- V adiazolythio, 2-benzoxazolylthio, etc.);
• a Z-aminoarylazoxy group e.g. Z-aminophenylazoxy, 2-
• a 2-amidoarylazoxy group e.g., Z-acetamidophenylazoxy, 2-acetamido-4-methylphenylazoxy, 2-acetamido-4- chlorophenylazoxy, 2-palmitamidophenylazoxy, 4- methoxy-2-palmitamidophenylazoxy, 4-chloro-2-palmitamidophenylazoxy, etc.
• a 2-aryltriazolyl group e.g., 2-benzotriazolyl, -chloro-2- benzotriazolyl, 5-hydroxy-2-benzotriazolyl, 4,7-dinitro-2- benzotriazolyl, 5-methyl-2-benzotriazolyl, 6-methoxy-2- benzotriazolyl, 4-carboxyethyl-2-benzotriazolyl, 4-sulfoethyLZ-benzotriazolyl, Z-naphthotriazolyl,4-methyl-2- naphthotriazolyl, 5-chloro-2-naphthotriazolyLS-hydroxy- Z-naphthotriazolyl, 5-nitro-2 naphthotriazolyl 5-sulfoethyl-Z-naphthotriazolyl, 4-amino-2-naphthotriazolyl, benzo[l,2-d:4,5-d']- bistriazolyl, etc
• the development inhibitor releasing couplers utilized in this invention can feature a S-pyrazolone coupler radical having the following general formula:
• R and R represent substituents of the type used in 5- pyrazolone couplers, for example, R, can represent a value given for R',;
• R can represent a member selected from the group consisting of an alkyl group, a carbamyl group (which can be substituted), an amino group'(which can be substituted with various groups such as one or two alkyl or aryl groups), an amide group, e.g., a benzamido group (which can be substituted), or an alkylamido group (which can be substituted), and
• Y represents a value given above for Formula III OH
• R R R and R can represent a substituent of the type used in phenolic couplers, for example, R and R each can represent a value given for R and in addition can represent a member selected from the group consisting of hydrogen, amino, carbonamido, sulfonamido, sulfamyl, carbamyl, halogen and alkoxy;
• DIR couplers include the following:
• the most useful DIR couplers are those which have a monothio group in the coupling position (e.g., Formula I, II and III above in which Y,, Y and Y represent a monothio group).
• Preferred DlR couplers have Formula I, II or III above wherein Y Y, and Y each represents a heterocyclic monothio radical in which the heterocyclic ring has from five to six atoms and at least one hetero atom selected from oxygen, sulfur and nitrogen, such as a hetero ring, containing from one to four hetero nitrogen atoms, e.g., a 5-tetrazolylthio group.
• any suitable light sensitive silver halide can be employed in the process of this invention.
• Suitable silver halides include silver chloride, silver bromide, silver chlorobromide, silver chloroiodjde, silver bromoiodide, and silver chlorobromoiodide.
• the silver halide grains canbe of any grain size, although particularly good results are obtained in the practice of this invention when fine grain silver halide is utilized.
• fine" silver halide grains refers to silver halide grains having an average grain size of up to about 0.5 micron, such as from about 0.1 to 0.5 micron.
• the silver halide emulsions can be either negative or direct positive emulsions. Especially good results are obtained with negative type silver halide emulsions.
• the photographic coating used in the invention is developed with photographic alkaline color developing solutions containing aromatic primary amino color developing agents.
• Such developing agents are well known in the art and typically are p-phenylenediamines.
• Suitable color developing agents include 3-acetamido-4-amino-N,N-diethylaniline, pamino-N-ethyl-N-B-hydroxyethylaniline sulfate, paminoethyl-BN,N-diethyl-p-phenylenediamine, 2-amino-5- diethylaminotoluene, N-ethyl-Bmethanesulfoamidoethyl- 3- methyl-4-aminoaniline, 4-amino-N-ethyI-3-methyl-N-Bsulfoethyl)aniline and the like.
• Bent et al. JACS 73, 3100-3125 (1951) for additional typical suitable color developing agents.
• fine grain silver halide is utilized in preferred embodiments of the invention.
• development is preferably conducted in the presence of silver halide solvent.
• Any suitable silver halide solvent can be utilized.
• Typical silver halide solvents useful herein are alkali thiosulfates, thiocyanates and cyanides; thiourea; thiocyanamine; and, ammonium hydroxide. Preferred results are obtained with sodium thiosulfate and sodium thiocyanate.
• auxiliary developer can be one typically employed as a black-and-white developing agent, such as a 3-pyrazolidone or an aminophenol.
• developers as l-phenyl- 4,4-dimethyI-B-pyrazolidone; l-phenyl-3-pyrazolidonc or methyl-p-aminophenol.
• concentrations of the various materials utilized in the processes of this invention are interrelated and vary with the type of particular compound used.
• concentration of DIR coupler needed to provide best results will depend upon the reactivity of the DIR coupler itself, and the effectiveness of development inhibition produced by the moiety split off from the DIR coupler upon reaction with oxidized color developing agent.
• concentration of the DIR coupler utilized will further be dependent upon the particular competing coupler, auxiliary developer and silver halide solvent. Generally speaking, good results can be obtained by employing concentrations of from about 0.1 to 20 percent, and preferably from about 1 to 15 percent of the DIR coupler based on the weight of the silver in the coating.
• Competing coupler is advantageously employed in the processing solution at concentrations of from about 0.05 to 20 g., and preferably from 1 to 15 g. per liter. Generally good results are obtained using silver halide solvent in a concentration of from 0.05 to 30 g., and preferably from 0.5 to 20 g. per liter of developer solution.
• Auxiliary developer can be employed within the general range of about 50 to 500 and preferably from to 300 mg. per liter of developer solution. In certain instances, good results can be obtained operating outside of any or all of these ranges.
• the emulsions employed in the practice of this invention can be coated on any suitable support, such as paper or polyethylene coated paper, or film base such as cellulose triacetate or poly(ethylene terephthalate).
• the emulsions can contain the chemical sensitizers, speed increasing compounds, plasticizers, hardeners and coating aids, and the silver halide may be dispersed in any of the binders, that are described and referred to in Graham et al. U.S. Pat. No. 3,046,129 issued July 24, 1962.
• the couplers used in the invention can be incorporated in the emulsion in any suitable manner, such as by the processes described in U.S. Pat. Nos. 2,322,027 or 2,801,171.
• a photographic element is prepared by coating a cellulose acetate support with a gelatin silver bromoiodide emulsion, the grains of which are between about 0.1 and about 0.5 micron in diameter, at a coverage of 190 mg. per square foot silver, 300 mg. per square foot gelatin.
• the coating also contains 9 mg. per square foot of the DIR coupler l-hydroxy-4-( lphenyl-S-tetrazolylthio)-2-(2-n-tetradecyloxy)naphthanilide, dissolved in suitable coupler solvent such as tri-o-cresyl phosphate.
• Samples of the film are exposed through a step tablet and to X-ray lines 10, 100 and 1000 microns in width. After exposure, thefilm is developed for 13 minutes at about 20 C. in the following developer composition:
• Color develo er 5.0 g. KBr 1.0 g. Nn,CO,(monohydr.) 50.0 g.' NaSCN 2.0 g. 3,6-disulfo-8-aminoJ- naphthol 2.0 g.
• EXAMPLE 2 The procedure of example 1 is repeated except that the DlR coupler is omitted from the emulsion, and the silver halide solvent, sodium thiocyanate, is omitted from the processing solution. The results are shown in table 2:
• EXAMPLE 3 The procedure of example 1 is repeated except that the DlR coupler is omitted from the emulsion coating. Processing is conducted in the presence of silver halide solvent and compet- The above able shows that the silver halide solvent in the developing solution in the absence of DlR coupler, afford no practical edge effects. The macrocontrast is somewhat higher than the microcontrast. The contrast is 3.5.
• EXAMPLE 4 The procedure of example 1 is repeated except that processing is conducted in the absence of silver halide solvent and competing coupler. Exposure and processing are exactly as described in example 1. The results are shown in table 4.
• EXAMPLE 5 The procedure of example 1 is repeated except that the silver halide solvent is omitted during processing. Exposure, processing and testing are exactly-as described in example 1.
• EXAMPLE 6 The procedure of example 1 is repeated except that the emulsion layer contains 130 mg. per square foot of the yellow dye forming coupler, a-pivalyl-a-(4-carboxyphenoxy)-2- chloro-S -['y-(2,4-di-t-amylphenoxy)butyramidolacetanilide dissolved in 65 mg. tricresyl phosphate.
• the element obtained in accordance with this example as excessively high fog.
• EXAMPLE 7 A photographic element is prepared similar to that in exampie 1 except that it contains on a cellulose acetate support a silver chlorobromide emulsion coated at 190 mg. silver per square foot and 154 mg. of gelatin per square foot. Upon exposure as described in example 1, processing in conventional black-and white developer and testing as in example 1, it is found that while the film has high contrast, its latitude is poor resulting in unsatisfactory continuous tone images. The density of the microimages at 10 and 100 micron widths are approximately the same, or somewhat lower, than that of the macroimage at 1000 microns.
• Examples 8 and 9 illustrate the improvement in reducing development time with a black-and-white developer being incorporated in the processing solution.
• EXAMPLE 8 The procedure described in example i is repeated except that the temperature of the developing solution is raised from C. to 38 C. By raising the temperature of the developing solution, the developing time is reduced from 13 to 3 minutes. An undesirably high fog level is obtained.
• EXAMPLE 9 The procedure described in example 8 is repeated except that the developing solution contains in addition 250 mg. of lphenyl-4,4-dimethyl-3-pyrazolidone per liter of solution. The development time is hereby further reduced from 3 to 1% minutes and the increase in fog obtained by the procedure according to example 8 is not observed.
• EXAMPLE 10 A sample ofa high-definition film comprising a single-layer gelatin silver chlorobromide emulsion containing 137 mg. of silver per square foot on a poly(ethylene terephthalate film base is exposed as in example i and conventionally black-andwhite developed, fixed, washed and dried. The gamma of the film is 2.6, and the microdensitometer traces give the results shown in table 6.
• the above table 7 shows the excellent ratio of microgamma to macrogamma, as well as the good edge effects obtained in the v practice of this invention.
• the contrast of the film is 3.2.
• EXAMPLE 12 The procedure of example H is repeated except that the coating does not contain DIR coupler. The results are shown in Table 8.
• a method for obtaining both high microcontrast and a low macrocontrast in developed photographic silver images comprising developing a photographic element containing an exposed fine grain silver halide photographic emulsion and development inhibitor-releasing coupler with a color develop ing agent in the presence of a competing coupler which reacts with said color developing agent to produce leuco or a soluble wash removable dye removing said soluble dye where produced, and obtaining an essentially colorless black and white image.
• said development inhibitor releasing coupler has a monothio group in its coupling position which, upon reaction with oxidized primary aromatic amino color developing agent, forms a diffusible mercaptan that inhibits development; and, said competing coupler forms diffusible dye on reaction with said oxidized aromatic primary amino color developing agent.
• Formula I (l) H Ri-JJ-+ i Formula II N CRa RsN /H ii Y Formula III 0H Rn- R10 wherein R, and R each represents a member selected from the group consisting of alkyl, aryl, and a heterocyclic group containing at least one hetero atom selected from oxygen, sulfur and nitrogen; X represents a member selected from the group consisting of cyano and carbamyl; R represents a member selected from the group consisting of alkyl, carbamyl, amino, amido, benzamido, and alkamido; R and R each represents a member selected from the group consisting of hydrogen, alkyl, aryl, a heterocyclic group containing at least one hetero atom selected from oxygen, sulfur and nitrogen, amino, carbonamido sulfonamido, sulfamyl, carbamyl, halogen and alkoxy; R and R when taken together, represents the atoms required to complete a benzo group, and when
• said development inhibitor releasing coupler is employed at a concentration of from about 0.1 to about 20 percent by weight of the silver in said coating; development is conducted with an aqueous processing solution containing the developing agent; said competing coupler is employed in the processing solution at a concentration of from about 0.05 to about 20 g. per liter; and, said silver halide solvent is employed in the processing solution at a concentration of from about 0.05 to 30 g. per liter.
• processing solution contains about 50 to mg. per liter of auxiliary black-and-white developing agent.
• the silver halide emulsion contains l-hydroxy-4-( l-phenyl-S-tetrazolythio )2-( 2 -ntetradecyloxy)naphthanilide dissolved in coupler solvent as a development inhibitor releasing coupler.
• developer solution contains an aromatic primary amino color developing agent, about 2 grams of 3,6-disulfo-8-amino-l-napthol per liter of developer solution, and about 2 grams sodium thiocyanate per liter of developer solution.
• a photographic process comprising:
• said developer solution contains an auxiliary developer selected from the group consisting of a 3-pyrazolidone developing agent and an aminophenol developing agent.

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• 1968
  • 1968-10-02 US US764599A patent/US3615499A/en not_active Expired - Lifetime
• 1969
  • 1969-10-01 DE DE1949591A patent/DE1949591C3/de not_active Expired
  • 1969-10-01 BR BR212917/69A patent/BR6912917D0/pt unknown
  • 1969-10-02 CH CH1485769A patent/CH514158A/fr not_active IP Right Cessation
  • 1969-10-02 BE BE739782D patent/BE739782A/xx unknown
  • 1969-10-02 FR FR6933586A patent/FR2019694A1/fr not_active Withdrawn
  • 1969-10-02 GB GB1264968D patent/GB1264968A/en not_active Expired

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