US3615499A

US3615499A - Photographic processes

Info

Publication number: US3615499A
Application number: US764599A
Authority: US
Inventors: Nicholas H Groet
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1968-10-02
Filing date: 1968-10-02
Publication date: 1971-10-26
Anticipated expiration: 1988-10-26
Also published as: CH514158A; BR6912917D0; DE1949591C3; BE739782A; DE1949591B2; DE1949591A1; GB1264968A; FR2019694A1

Abstract

Exposed photographic silver halide emulsions containing development inhibitor releasing coupler are processed in the presence of primary aromatic color developing agent and a competing coupler which produces substantially no permanent dye in the emulsion.

Description

United States Patent Inventor Nicholas R. Groet Rochester, N.Y.

Appl. No. 764,599

Filed Oct. 2, 1968 Patented Oct. 26, 1971 Assignee Eastman Kodak Company Rochester, N.Y.

PHOTOGRAPHIC PROCESSES 12 Claims, No Drawings U.S. Cl 96/55, 96/56.5, 96/56.6 Int. Cl G03c 7/00 Field of Search 96/55, 22, 48, 66.3

Primary Examiner-Norman G. Torchin Assistant ExaminerAlfonso T. Suro Pico Anorneys--W. H. J, Kline, .l. R. Frederick and O. H. Webster ABSTRACT: Exposed photographic silver halide emulsions containing development inhibitor releasing coupler are processed in the presence of primary aromatic color developing agent and a competing coupler which produces substantially no permanent dye in the emulsion.

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.

Still other objects of this invention will be apparent from the disclosure herein and the appended claims.

In accordance with this invention, an improvement is provided 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.

in preferred embodiments of the invention, the photographic silver halide emulsion layer comprises fine silver halide grains, and the development is conducted in the presence ofa silver halide solvent.

in another embodiment of this invention, the novel processes described above are enhanced by conducting development in the presence of an auxiliary developer.

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.

Competing couplers which form colorless reaction products with primary aromatic amino color developing agents are described by Puschel, On the Chemistry of White Couplers" Agfa-Gevaert A.G. Mitteilangen aus den Forschingslaboratorien der Agfa-Gevaert A.G.. Spinger Verlay, 1954, pages 352-367; French Pat. No. 1,340,552 Sept. 9. i963); and British Pat. No. 907,274 1962) l962)**which disclosures are incorporated herein by-reference.

Particularly good results are achieved in the practice of this invention with the competing coupler 4-carboxy-2, 6- dihydroxypyridine (citrazinic acid or CZA) and 3,6-disulfo-8- amino-l-naphthol (ll-acid). Other specific useful couple compounds that can be employed are listed below: I

2-amino-5-naphthol-7-sulfonic acid--.l-acid l,8-dihydroxynaphthalene disulfonic acid-chromotropic acid 1-naphthol-3,6,8-trisulfonic acid l-naphthol-Z-sulfonic acid p-(w-Benzoylacetamino) benzene-sulfonic acid 2,4-di-nitrophenylacetic acid 1-amino-8 -naphthol-2 ,4disulfonic acid l-napthol-4,8-disulfonic acid l-p-sulpphenyl-3-methyl-5 -pyrazolone l-phenyl-3-meta-sulfobenzamido-S -pyrazolone l-naphthol-5-sulfonic acid The competing coupler can be incorporated in the emulsion layer itself if desired. However, it is preferred to employ the competing coupler in the developer solution.

The term 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. As is well known in the art, 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.

wherein denotes the coupling position).

Development inhibitor-releasing (DIR) couplers which can be utilized herein can be represented by the general formula:

wherein 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.

An especially useful class of. open-chain ketomethylene coupler radicals is described in Formula 1 below:

Formula I I R1-?Yl wherein R, and X, represent substituents of the type used in open-chain DIR ketomethylene couplers. For example R, can

represent an alkyl group (which can be substituted and preferably has from about six to 22 carbon atoms); an aryl group (preferably a phenyl or naphthyl group); or, a heterocyclic group (preferably a carbon containing heterocyclic radical which contains from five to six atoms in the heterocyclic ring, which ring contains at least one hetero oxygen, sulfur or nitrogen atom); X, can represent a member selected from the group consisting of cyano and carbamyl (which can be substituted); and, 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 nitro, halogen (chlorine, bromine, iodine, fluorine), lower alkyl, lower alkylamido, lower alkoxy, lower alkylsulfonamido, achloroacetylthio, lower alkylcarbamyl amino, etc., typical monothio groups representing the above include 2- aminophenyl, 2-nitrophenyl and a heterocyclic group (e.g. 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.);

2. a Z-aminoarylazoxy group (e.g. Z-aminophenylazoxy, 2-

amino-4-chlorphenylazoxy, etc.);

3. 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.);

4. 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 coupler forms a diffusible mercaptan when Y represents (1) above, and a diffusible aryltriazole when Y represents (2), (3) or (4) above, upon reaction with oxidized color developing agent.

The development inhibitor releasing couplers utilized in this invention can feature a S-pyrazolone coupler radical having the following general formula:

Formula II wherein 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 wherein 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; R and R when taken together, can represent the carbon atoms necessary to complete a benzo group, which benzo group can be substituted with any of the groups given for R and R and, when taken separately, R and R can each independently represent a value given for R and R and Y represents a value given above for Y,.

Representative DIR couplers include the following:

1. a-Benzoyl-a-(2-nitrophenylthio)-4-[N-(y-phenylpropyU- N-(p-tolyl)-sulfamyl]acetanilide a-Benzoyl-a-( 2-benzothiazolylthio )-4-[ N-( y-phenylpropyl)-N-(p-tolyl)sulfamyllacetanilide 3, a-{ 3-[a-(2,4-di-tert-amylphenoxy)butyramidol-benzoyl}-a Z-meihoxyacetanilide 4. a-l3-[y-(2,4-ditert-amylphenoxy)butyramido1-benzoyl }-a- 2-be'nzoxazolylthio) 2-methoxyacetanilide 5. a-Benzoyl-a-M l-( 3-phenyl)-5 -tetrazolythio]stearam ido acetanilide 6. a-{3-[a-(2,4-di-tert-arnylphenoxy)butyrarnido]benzoyl}- a-(Z-aminoplmnylazoxy)-2-methoxyacetanilide 7. a-{3-['y-(2 4-di-tert-amylphenoxy)butyramido]-benzoyl-a- Q-amino-jgn ethylphenylazoxy)-2-rnethoxy-acetanilide s. a-(5-Chloro-2 beiizotriazolylyapivzfiyl-fla-(2,4-di-tertamylphenoxy)propylamido]-2-chloroacetanilide 9. a-(4,7-Dinitro-2-benzotriazolyl)-a-pivalyl-3,6-dichloro-4- (N-methyl-N-octadecylsulfamyl)acetoacetanilide 10. a-( 6-Chloro-5-methoxy-2-benzotriazoyl )-a-pivaly2- chloro-5-[a-( 3-pentadecyl-4sulfophenoxy)-butyremido ]acetanilide, sodium salt 1 l. l-Phenyl-3-octadecylamino-4-[2-phenyl-5( l ,3,4)-oxadiazolylthio]-5-pyrazolone l2. l-{4-[y-(2,4di-tert-amylphenoxy)butyramidol-phenyl 3-ethoxy-4-( l-phenyl-5-tetrazolylthio-5-pyrazolone l3. 1-{4-[a-(Bpentadecylphenoxy)butyramidolphenyll -3- ethoxy-4-( l-phenyl-5-tetrazolylthio )-5-pyrazolone l4. l-(2,4,6-trichlorophenyl)-3-{4-[a-(2,4-di-tertamylphenoxy)butyramidolanilino -4-(l-phenyl-5- tetrazolylthio)- 5-pyrazolone l5. l-Phenyl-3-octadecylamino-4-( l-phenyl-5-tetrazolylthio 5-pyrazolone l6. l[4-( 4-tert-butylphenoxy)phenyl]-3-phenyl-4-( l-phenyl- S-tetrazolylthio) -5-pyrazolone 17. l-[4-(4-tert-butylphenoxy)phenyl]-3-[ a-( 4-tert-butylphenoxy)propionamido]-4-( S-phenyll ,3 ,4-oxadiazolyl -2- thio)-5-pyrazolone l8. 1-[4-(4-tert-butylphenoxy )phenyl]-3-[a-(4-tert-butylphenoxy)propionamido]-4-(2-nitrophenylthio)-5- pyrazolone l9. l-[4-(4-tert-butylphenoxy)phenyll-3-la-(4'tert-butylphenoxy)propionamido]-4-[ l-(4-methoxyphenyl)- 5- tetrazolylthio]-5-pyrazolone 20. l -[4-(4-tert-butylphenoxy )phenyl1-3-[a4-tert-butylphenoxy)propionamido1-4-(.2*benzothiazolylthio)-5- pyrazolone 21. l-[4-tert-butylphenoxy)phenyl]-3-[ a-(4-tert-butylphenoxy)propionamido]-4-(2-nitrophenylthio5- pyrazolone l-[4-(4-tert-butylphenoxy)phenyl]-3-[a-(tert-bu- 22. tylphenoxy)propionamido]-4-(2-benzoxazolylthio pyrazolone 23. 1-(2,4-dichloro-6-methoxyphenyl)-3-[a-(3-pentadecylphenoxy)acetamido]-4-( 1-phenyl5-tetrazolylthio)-5- pyrazolone 24. l-Phenyl-3-octadecyl-4-( l-phenyI-5-tetrazolylthio)-5- pyrazolone 25 l-Phenyl-3-[-(2,4-di-tert-amylphenoxy)acetamido]-4-( lphenyl-S-tetrazolylthio)-5-pyrazolone 26. l-Phenyl-3-['y-(2,4-di-tertamylphenoxy)butyramido1-4- l-phenyI-5-tetrazolylthio)-5-pyrazolone 27. l-Phenyl-3-(3,5-didodecyloxybenzamido)-4-(2- nitrophenylthio)-5-pyrazolone 28. l-Phenyl-3-[a-(2,4-di-tert-amylphenoxy)acetamido]-4- (2-aminophenylazoxy)-5pyrazolone 29. 4-Benzotriazolyl-3-pentadecyl-l-phenyl-S-pyrazolone 30. 4-Benzotriazolyl-l-(2,4,6-trichlorophenyl)-3-[3-{a-(2,4- di-t-amylphenoxy)acetamido }benzamido]-5-pyrazolone 31. 4-(5-Methoxy-Z-benzotrizizolyl)-3-pentadecyll -phenyl-5- pyrazolone 32. 4-(4Carboxy,2-benzotriazolyl)-l-(2,4,6-trichlorophenyl- 3-pentadecyI-5-pyrazolone 3 3 l-I-Iydroxy-4-( 2-nit'rophenylthio )-N-[8-(2 ,4-di-tertamylphenoxy)butylI-Z-naphthamide 34. l-Hydroxy-4-(2-benzothiazolylthio)-N-[8-(2,4-di-tertamylphenoxy)butyl]-2-naphthamide 35. l-Hydroxy-4-( l-phenyI-5-tetrazolylthio)-N-[8-(2,4-ditert-amylphenoxy)butyl]-2-naphthamide 36. l-Hydroxy-4-(2-benzothiazolylthio)-N-octadecyl-3, 5" dicarbOXy-Z-naphthanilide 37. I -Hydroxy-4-( 1-phenyl-5-tetrazolylthio)-2-tetradecyloxy- Z-naphthanilide 38. l-Hydroxy-4-[ l-(4-methoxyphenyl)-5-tetrazolylthiol-N- [8-( 2,4-di-tert-amylphenoxy)butyl-2-naphthamide 39. l-I-Iydroxy-4-(5-phenyl-l,3,4-oxadiazolyl-2-thio) N-IS- (2,4-di-tert-amylphenoxy)butyl]-2-naphthamide 40. 5-Methoxy-2-[a-(3-n-petadecylphenoxy)butyramido1-4- l'phenyl-5-tetrazolylthio)phenol 41. l-I-lydroxy-4-(2-amino-4-methylphenylazoxy-N-[8-(2,4- di-tert-amylphenoxy)butyl]-2-naphthamide 42. 4-(2-Benzotriazolyl)-2-[8-(2,4-diamylphenoxybutyl)]-1- hydroxynaphthamide 43. l-I-l ydroxy-4-( 6-nitro-2-benzotriazolyl )-N-[ 8-( 2 ,4-di-tamylphenoxy)butyl]-2naphthamide 44. 5-Methoxy-2-[a-(3-pentadecylphenoxy)butyramidol-4- (S-chloro-2-benzotriazolyl)phenol 45. 5-Methoxy-2-[a-(3-pentadecylphenoxy)butyramido1-4- (6-chloro-5-methoxy-Z-benzotriazolyl)phenol Couplers 1 through 5, 11 through 27, 33 through 40 are described in Barr U.S. Pat. No. 3,227,554. Couplers 6, 7, 28 and 41 are prepared by methods similar to those disclosed in U.S. Pat. No. 3,148,062. Couplers 8 through 10, 29 through 32 and 42 through 45 are described by Sawdey U.S. Pat. application Ser. No. 674,090, filed Oct. 10, I967. The couplers referred to in the immediate paragraph are the DIR couplers listed above.

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. As used herein and in the appended claims, 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. Reference is also made to Bent et al., JACS 73, 3100-3125 (1951) for additional typical suitable color developing agents.

As indicated heretofore, fine grain silver halide is utilized in preferred embodiments of the invention. When fine grain silver halide emulsions are utilized in the processes of memvention, 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.

In some instances, it is desirable to achieve satisfactory development at relatively high temperatures, such as about 40 C. up to 60 C., in relatively short periods, such as l, 2 or 3 minutes. It has been found as an additional feature of the present invention that such high temperatures and short development times can be achieved by utilizing an auxiliary (i.e., noncolor) developing agent. The auxiliary developer can be one typically employed as a black-and-white developing agent, such as a 3-pyrazolidone or an aminophenol. Especially useful results are obtained with such developers as l-phenyl- 4,4-dimethyI-B-pyrazolidone; l-phenyl-3-pyrazolidonc or methyl-p-aminophenol.

The optimum concentrations of the various materials utilized in the processes of this invention are interrelated and vary with the type of particular compound used. For example, the 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. The 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.

The following examples are included for a further understanding of the invention.

EXAMPLE I 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:

Water 950 ml. Benzyl alcohol 3.8 ml. Sodium polyphosphate 2.0 g. Sodium sulfite (desicc.) 2.0 g. 10% NaOH Soln. 5.5 ml.

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.

Water to 1 liter p1 l=10.75

4-Amino-3 methyl-N-ethyl-N-fl-(methanesulfonamido)ethyl- 40 aniline sesquisulfate hydrate The element is then washed, fixed, washed again and dried. Microdensitometer traces of the three images are made and the maximum density at the edge and the center of the three lines are read (at 1.0 above gross fog) and the relative densities are shown in table 1 below. It will be noted that in this example, as in the following examples, the center and the edge of he IO-micron line image have essentially the same densities.

TABLE 1 Image Width D max 1000;]. 100 to,

. Edge ol'image 1.1 1.2 1.3 Center of image 0.7 0.9 1.3

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:

TABLE 2 image Width D max. 1000 4. 10

Edge of image 0.6 0.6 0.5 Center of image 0.6 0.6 0.5

The above results show that this element is entirely unsuited to the recording of fine line images. This film actually has lower microgamma than macrogamma (showing inability to record continuous tone images satisfactorily). There are substantially no edge effects. The contrast is 4.2.

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.

TABLE 4 Image Width D max. 1000p. 100;) I011 Edge of image 0.2 0.3 0.4 Center of image 0.2 0.3 0.4

The above results show that omission of competing coupler and silver halide solvent in developing solution resulted in only no practical edge effects with extremely low image example being obtained. The contrast is undesirably low at 0.20.

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.

5 The results are set out in table 5 below.

TABLE Image Width D max. 1000 100 image Width D iu 5 Edge of image 0.9 0.9 0.0 Center of image 0.9 0.9 0.8

Edge ofimage 1.0 l.l 1.0 Center of image 0.7 0.8 [.0

The above results show that the presence of DIR coupler in the emulsion together with competing coupler in the developing solution results in excellent edge effects, and higher microgamma than macrogamma. The contrast of the film is 0.65. Edge effects are further enhanced by the presence of silver halide solvent, as shown in example 1 above.

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. When the example is repeated using the less reactive yellow dye forming coupler, a-pivalyl-Z-chloro-S-[y-(2,4-di-tamylphenoxy)butyramidol-acetanilide, the image contrast is far too low to be useful in recording fine line images.

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.

TABLE 6 The results in table 6 show that the macrogamma is undesirably higher than the microgamma.

EXAMPLE 1 l TABLE 7 Image Width D max. I000 100 [0 Edge of image 1.4 1.5 1.7 Center of image 0.9 l .0 L7

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.

TABLE 8 image Width D max. 1000 [0 Edge of image 1.3 l 1 Center of image [.3

The above results demonstrate the undesirably high macrogamma (which means shortened exposure latitude) with moderate improvement in edge effects. The contrast is 4.5.

The invention has been described in detail with particular reference to preferred embodiments thereof, but, it will be understood that variations and modifications can be effected within the spirit and scope of the invention described hereinabove and in the appended claims.

1. 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.

2. The method of claim 1 wherein said development is conducted in the presence of an auxiliary black-and-white developing agent.

3. The method of claim 1 wherein said development is conducted in the presence of a silver halide solvent.

4. The method of claim 1 wherein 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.

5. The method of claim 4 wherein said development inhibitor releasing coupler has one of the following structural formulas:

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 taken separately, each represents a value selected from those given for R and R and, said Y Y and Y each represents a monothio group selected from an orthoaminosubstituted arylmonothio group; an orthonitro-substituted arylmonothio group; and, a heterocyclic radical containing at least one hetero atom selected from oxygen, sulfur and nitrogen, to complete said coupler.

6. The method of claim 5 wherein 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.

7. The method as defined in claim 6 wherein said processing solution contains about 50 to mg. per liter of auxiliary black-and-white developing agent.

8. The method of claim 1 wherein 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.

9. The method of claim 8 wherein the 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.

10. The process of claim 8 wherein said development is conducted in the presence of about 250 mg. per liter of developer solution of l-phenyll ,4-dimethyl-3-pyrazolidone.

l l. A photographic process comprising:

A. contacting a photographic element having an exposed fine grain silver halide photographic emulsion with an average diameter of from 0.1 to 0.5 micron and containing a development inhibitor-releasing photographic coupler selected from the group consisting of:

a. a S-pyrazolone b. an open chain ketomethylene, and c. a phenolic photographic coupler, said inhibitor-releasing coupler having a monothio group in coupling position, with a photographic developer solution containing 1. an aromatic primary amino color developing agent;

and 2. about 0.05 to 30 grams ofa silver halide solvent per liter of developer solution, the development step being effected in the presence of a competing coupler which reacts with oxidized color developing agent to produce a leuco or a soluble wash remova ble dye, and

B. washing out the soluble dye where produced to obtain an essentially colorless black and white image.

12. The photographic process defined in claim 11 wherein said developer solution contains an auxiliary developer selected from the group consisting of a 3-pyrazolidone developing agent and an aminophenol developing agent.

3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3 5 A9? d February 21 1972 Patent No. Date Inventor) Nicholas H Groet It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 73, after "Pat. No. l,3 lO,522" and before "Sept." insert a parenthesis line 7 4, after "907,72U" and before "1962" insert a parenthesis and after "1962? (first occurrence, delete "l962)**.

Column 3, line 13, replace "2" with l-- line 3, replace "2-phenyl-5-l,3, l)-ox-" with -p y 5( ,3, lines 36 and 37, replace both lines with a 2- aminoarylazoxy group (e.g. 2-amino-M- methylphenylazoxy, 2-aminopheny1azoxy, 2- amino-H-chlorphenylazoxy, etc.)

Column 4 lines 30-31 replace both lines with 3 6-; {3-1,};

(2,M-di-tert-amylphenoxy)butyramidg/ benzoyl} L 2nitrophenylthio-2-methoxyacetanilide;

line 32, replace ditert-" with --ditert line 33, after "(2-benzoxazolylthio)" insert a hyphen line 3 4 replace entire line with 5 o Benzoyl-0 T(3 phenyl)5-tetrazolylthi /stearamido line 10, replace ;pivalyl-" with L-pivalylalso after "-5" insert a hyphen lin L15 replace "pivaly" with pivalylline 48, after "2-phenyl-5" insert a hyphen line 50 after T 2 l insert a hyphen line 51, after "S-tetrazolylthio" insert a parenthesis line 55, after "anilinojf delete the first hyphen;

Pa e l of 2 a es L 8 P E J UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. a Dated February 21 7 Nicholas H. Groet PAGE 2 Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 57, after "5-tetrazolylthio" insert a parenthesis and a hyphen line 70 after "A? insert a hyphen followed by a parenthesis line 7, after *2-nitorphenylthio" insert a parenthesis and a hyphen line 75, replace "pyrazOlone" with pyrazolone-.

Column 5, line 2, after "benzoxazolythio" insert a parenthesis and a hyphen line 5, after "-U-(l-phenyl" insert a hyphen line 9, after "3-K" insert line 22, replace entire line with -32. l-(U-Carboxy- 2-benzotriazolyl)-l-(2, l,6-trichlorophenyl).

Column 6 line 15 after "aminoethyl-fi insert -hydroxyaniline line 16 after "N-ethyl-fl insert a hyphen line 17, after "-N-fl insert a hyphen Column 7, line 51, replace "he" with the--.

Signed and sealed this 13th day of June 1972.

(SEAL) Attest:

EDWARD M. FLETCHER,JR.

Attesting Officer ROBERT GOTTSCHALK Commissionerof Patents

Claims

2. The method of claim 1 wherein said development is conducted in the presence of an auxiliary black-and-white developing agent.
2. about 0.05 to 30 grams of a silver halide solvent per liter of developer solution, the development step being effected in the presence of a competing coupler which reacts with oxidized color developing agent to produce a leuco or a soluble wash removable dye, and B. washing out the soluble dye where produced to obtain an essentially colorless black and white image.
3. The method of claim 1 wherein said development is conducted in the presence of a silver halide solvent.
4. The method of claim 1 wherein 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.
5. The method of claim 4 wherein said development inhibitor releasing coupler has one of the following structural formulas:
6. The method of claim 5 wherein 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.
7. The method as defined in claim 6 wherein said processing solution contains about 50 to 100 mg. per liter of auxiliary black-and-white developing agent.
8. The method of claim 1 wherein the silver halide emulsion contains 1-hydroxy-4-(1-phenyl-5-tetrazolythio)2-(2''-n-tetradecyloxy)naphthanilide dissolved in coupler solvent as a development inhibitor releasing coupler.
9. The method of claim 8 wherein the developer solution contains an aromatic primary amino color developing agent, about 2 grams of 3,6-disulfo-8-amino-1-napthol per liter of developer solution, and about 2 grams sodium thiocyanate per liter of developer solution.
10. The process of claim 8 wherein said development is conducted in the presence of about 250 mg. per liter of developer solution of 1-phenyl-1,4-dimethyl-3-pyrazolidone.
11. A photographic process comprising: A. contacting a photographic element having an exposed fine grain silver halide photographic emulsion with an average diameter of from 0.1 to 0.5 micron and containing a development inhibitor-releasing photographic coupler selected from the group consisting of: a. a 5-pyrazolone b. an open chain ketomethylene, and c. a phenolic photographic coupler, said inhibitor-releasing coupler having a monothio group in coupling position, with a photographic developer solution containing
12. The photographic process defined in claim 11 wherein said developer solution contains an auxiliary developer selected from the group consisting of a 3-pyrazolidone developing agent and an aminophenol developing agent.