US3000736A - Photographic silver halide diffusion transfer process - Google Patents
Photographic silver halide diffusion transfer process Download PDFInfo
- Publication number
- US3000736A US3000736A US724815A US72481558A US3000736A US 3000736 A US3000736 A US 3000736A US 724815 A US724815 A US 724815A US 72481558 A US72481558 A US 72481558A US 3000736 A US3000736 A US 3000736A
- Authority
- US
- United States
- Prior art keywords
- silver
- silver halide
- image
- stratum
- nitroindazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/02—Photosensitive materials characterised by the image-forming section
- G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
- G03C8/06—Silver salt diffusion transfer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/24—Photosensitive materials characterised by the image-receiving section
- G03C8/243—Toners for the silver image
Definitions
- This invention relates to a photographic process of the silver halide diffusion transfer type wherein undeveloped silver halide of an emulsion layer is transfererd as a silver complex imagewise by imbibition to a silver precipitating or nucleating layer generally to form a positive image therein.
- this type of process can be carried out by developing an exposed emulsion layer with a developing solution containing a silver halide solvent after which the emulsion layer is placed into contact with a second element carrying a silver precipitating layer to cause the undeveloped silver halide to transfer imagewise as a silver complex to the second element and form an image thereon.
- the process has also been carried out utilizing a multilayer element such as one carrying on a support two gelatin layers of different solubility, for example, the layer next to the support containing a silver precipitating agent and being harder than the outer gelatin layer which is a gelatin emulsion layer containing silver halide.
- a multilayer element such as one carrying on a support two gelatin layers of different solubility, for example, the layer next to the support containing a silver precipitating agent and being harder than the outer gelatin layer which is a gelatin emulsion layer containing silver halide.
- a multilayer element comprising a silver precipitating stratum on a support and over this-stratum a silver halide emulsion in which the silver halide is uniformly dispersed in an alkalisoluble, acid-insoluble carboxylated cellulose derivative such as cellulose ether phthalate.
- the silver halide diffusion transfer processes such as described above have a common disadvantage; they tend to produce argental images which are brown in color rather than being neutrally toned as is desired. To alleviate this condition it has previously been proposed to carry out the diffusion transfer processes in the presence of organic compounds such as sulfur-containing heterocyclic compounds which cause the formation of neutrally toned images.
- the objects of my invention are accomplished by incorporating the nitroindazoles in developer compositions, emulsion layers, silver precipitating layers or other layers of sensitive elements used in the diffusion transfer processes and using such developers and elements in diffusion transfer processes.
- Example 1 To 183 grams of silver chloride emulsion containing 0.05 mole of silver halide were added 50 cc. of 4% aqueous gelatin solution, 16 cc. of water, 20 cc. of 0.75% aqueous S-nitroindazole solution, 10 cc. of 7.5% aqueous saponin solution and 0.76 cc. of 20% formaldehyde solution.
- This emulsion was coatedon a light-weight photographic paper at 500 square feet per mole of silver halide. The coating was exposed, treated with the following developer solution and squeezed into contact with the following receiving sheet in a commercially available machine designed for the silver halide diffusion transfer process.
- the emulsion-coated paper was stripped from the receiving sheet thirty seconds after the sandwich emerged from the machine.
- the positive image obtained on the receiving sheet had a dark brown-black color as compared to a greenish-brown color when the S-nitroindazole was omitted from the control emulsion:
- Receiving sheet A solution, 2800 g., containing: 4% gelatin, 0.00135 mole ZnS, 0.000135 mole Zn(NO 18 g. Na SO 18 g. Na S O -5H O, cc. 7.5% saponin,
- Example 2 An emulsion was prepared in the manner of Example 1 except using 10 cc. of 1% potassium bromide and 10 cc. of 1% S-nitroindazole in place of the 20 cc. of 0.75% S-nitroindazole. The emulsion was coated and tested as described in Example 1 producing on the receiving sheet a very black image whereas the image tone was greenish-brown when the control emulsion contained only the potassium bromide and no S-nitroindazole.
- Example 3 An emulsion was prepared in the manner of Example 1, using 10 cc. of 1% 3-methylbenzothiazolium methyl sulfate plus 10 cc. of 1% S-nitroindazole in place of the 20 cc. of 0.75% S-nitroindazole. When coated and tested as described in Example 1, this produced a very black image, whereas with just the benzothiazolium salt, the image was reddish-brown, and when both the B-methylbenzothiazolium salt and the S-nitroindazole were omitted, the image was greenish-brown.
- Example 4 This example is representative of methods for employing the eifective indazoles for producing dark images in the processes of the Yackel et al.
- U.S. patent application Serial No. 586,705 filed May 23, 1956, which processes employ an element having a silver halide emulsion containing an alkali-soluble, acid-insoluble carboxylated cellulose derivative vehicle, such as a phthalate of ethyl cellulose or of cellulose acetate, coated upon a silver precipitating layer, and the element after exposure is processed with a developer solution containing silver halide developing agent and silver halide solvent in the presence of one or more of the three mentioned nitroindazoles to form an argental image in the silver precipitating layer after which the emulsion layer is washed oil of the silver precipitating layer.
- an alkali-soluble, acid-insoluble carboxylated cellulose derivative vehicle such as a phthalate of ethyl cellulose or of cellulose acetate
- the sensitive element may be prepared by taking 170 cc. of a washed chlorobromide emulsion containing 0.03 mole silver halide, approximately 0.6 g. gelatin, and 87 cc. of a 6% solution of the ammonium salt of cellulose ether phthalate, and adding 10 cc. of 0.46% aqueous nitroindazole solution. This preparation is then coated on a zinc sulfide silver precipitating layer prepared as described in Example 1 of the Yackel et al. invention above by the reaction of sodium sulfide with zinc nitrate.
- the resulting element was then exposed to a subject and developed for 60 seconds at 68 F. in a developer of the following composition:
- a coating was prepared and processed in the manner of Example 4, using 1.53 g. of 5,6-dinitroindaz0le per mole of silver in the emulsion in place of S-nitroindazole. In this case, the positive image had a brown-black tone.
- Example 6 A coating was prepared in the manner of Example 4, using 1.53 g. of 6-nitroindazole per silver mole in the emulsion in place of S-nitroindazole. In this case, the image was blue-black as in Example 4.
- Example 7 When the process of Example 4 was carried out with 7-nitroindazole in place of 5-nitroindazole, the silver image obtained in the positive print was reddish-brown in color.
- Example 8 The sensitive element described in Example 4 was processed as described except using the following developing solution:
- Example 9 The sensitive element described in Example 4 was processed as described except using the following developing solution:
- Example 10 The sensitive element of Example 4 was used having the cellulosic emulsion coated upon the zinc sulfide precipitating layer, except that the S-nitroindazole was ormtted from the emulsion. Processing was carried out as described in Example 4 but using the following developer solution:
- Example 11 The following developer solution is also suitable for producing neutral toned images in the silver halide diifusion transfer processes such as described in Example Water to 1 liter.
- the silver precipitating layer in which the argental image is formed may contain as silver precipitating agents sulfides, selenides, polysulfides, polyselenides, thiourea, mercaptans, stannous halides, heavy metals and heavy metal salts, and fogged silver halide.
- Silver precipitating agents sulfides, selenides, polysulfides, polyselenides, thiourea, mercaptans, stannous halides, heavy metals and heavy metal salts, and fogged silver halide.
- Heavy metal sulfides such as lead, silver, zinc, antimony, cadmium and bismuth sulfides are useful, particularly the sulfides of lead and zinc alone or in admixture, or complex salts of these with thioacetamide, dithiooxamide, or dithio-biuret.
- the heavy metals include silver, go-ld, platinum, palladium and mercury preferably in the
- the silver precipitating agents may be applied directly to a support such as paper, or to suitably subbed cellulose derivative supports and synthetic polymer supports from solutions or dispersions of the silver precipitating agents in a colloid vehicle such as gelatin.
- a colloid vehicle such as gelatin.
- the colloid vehicle of the silver precipitating layer of the invention of Yackel et al. is necessarily insoluble in the solution used for removing the carboxylated cellulose derivative emulsion layer in the final stage of the process. If gelatin is used, it should be hardened.
- the nitro indazoles When employed in the invention of Yackel et al., they may be employed in any of the hydrophilic layers of the sensitive element.
- the silver halide emulsion can be applied directly over the silver precipitating layer, but preferably a thin layer of one of the alkali-soluble carboxylated cellulose derivatives, e.g., a dibasic acid ester of cellulose ethyl ether is first applied followed by the emulsion layer.
- This thin layer is not absolutely essential; however, it has been found to facilitate the clean removal of the emulsion from the silver precipitating layer.
- the silver halide component of the mentioned emulsions is not especially critical and can include various silver halides and mixtures of silver halides such as silver bromoiodide, silver chloride or silver bromide optically sensitized in the usual manner.
- the emulsions may be developing-out emulsions designed for development to negative images in which case the image obtained in the silver precipitating layer is a positive with respect to the original subject.
- the emulsion can be of the direct positive type with the result that the silver image developed in the emulsion is a positive and the image in the silver precipitating layer a negative in respect to the original subject.
- the procedures of Leermakers U.S. Patent 2,184,013 and Kendall et al. U.S. Patent 2,541,472 are useful in conferring the direct positive characteristics to the emulsion.
- the silver halide developing solution used for initiating development of the exposed sensitive elements described, in the presence of the mentioned nitroindazoles, is not especially critical and can be of the conventional type used for developing films or papers with the exception that a silver halide solvent such as hypo, sodium thiocyante or ammonia is present in the quantity required to form the soluble silver precipitating layer.
- Silver halide develop ing agents useful in the developing solution include hydroquinone, monomethyl-p-aminophenol sulfate, aminophenols, halogenated hydroquinones, toluquinone, p-hydroxyphenyl aminoacetic acid, 3-pyrazolidone developing agents such as l-phenyl-3-pyrazolidone and mixtures of these developing agents.
- the silver halide developing agent may be present in the emulsion layer or developing solution. In the former case it is preferred to use a substantially non-diifusing developing agent such as the dihydroxy diphenyls e.g. 3,4-dihydroxydiphenyl in the emulsion layer.
- the nitroindazoles may be used in the emulsion layer in quantities of about 0.5 to 4.0 gram per mole of silver halide. When the nitroindazoles are employed in the developer solution, about 0.1 to 2.0 grams per liter are satisfactory.
- These compounds may be used in emulsion layers employed in silver halide ditfusion transfer processes alone or in conjunction with other compounds such as the nitroindazoles as described in Example 3 above or in combination with 2-mercapto-5-phenyl-l-oxa-3,5-diazole.
- a method of forming a photographic image which comprises exposing to a subject an element including a support, a silver precipitating stratum on the support, and adhered to said stratum a light-sensitive emulsion layer containing silver halide uniformly dispersed in an alkalisoluble acid-insoluble dibasic acid ester of a member of the class consisting of cellulose ethyl ether and cellulose acetate, developing a latent image in the emulsion layer with a silver halide developing solution containing a silver halide developing agent and a silver halide solvent in contiguity with a member of the class consisting of S-nitroindazole, 6-nitroindazole and 5,6-dinitroindazole to form a silver image and imagewise distribution of a soluble silver complex in the emulsion layer, allowing a portion of said silver complex to diffuse imagewise to said silver precipitating stratum and the silver of said portion of silver complex to be precipitated in said stratum as a silver image of improved
- a method of forming a photographic image which comprises exposing to a subject an element including a support, a silver precipitating stratum 0n the support, and adhered to said stratum a light-sensitive emulsion layer containing silver halide uniformly dispersed in an alkalisoluble acid-insoluble phthalate of a member of the class consisting of ethyl cellulose and cellulose acetate, developing a latent image in the emulsion layer with a silver halide developing solution containing a silver halide developing agent and a silver halide solvent in contiguity with a member of the class consisting of S-nitroindazole, 6-nitroindazole and 5,6-dinitroindazole to form a silver image and an imagewise distribution of a soluble silver complex in the emulsion layer, allowing a portion of said silver complex to diffuse imagewise to said silver precipitating stratum and the silver of said portion of silver complex to be precipitated in said stratum as a silver image of improved tone,
- an argental image is formed therein by interaction of said diffused silver halide and a silver precipitating agent,- the improvement in which said interaction takes place in association with 5,6-dinitroindazole to improve the tone of said argental image.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE577129D BE577129A (fr) | 1958-03-31 | ||
US724815A US3000736A (en) | 1958-03-31 | 1958-03-31 | Photographic silver halide diffusion transfer process |
DEE17040A DE1064807B (de) | 1958-03-31 | 1959-01-22 | Photographisches Silbersalz-Diffusionsuebertragungsverfahren |
GB10504/59A GB907146A (en) | 1958-03-31 | 1959-03-26 | Improvements in photographic reproduction processes |
FR790623A FR1221438A (fr) | 1958-03-31 | 1959-03-27 | Nouveau procédé pour l'obtention d'images photographiques |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US724815A US3000736A (en) | 1958-03-31 | 1958-03-31 | Photographic silver halide diffusion transfer process |
Publications (1)
Publication Number | Publication Date |
---|---|
US3000736A true US3000736A (en) | 1961-09-19 |
Family
ID=24912027
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US724815A Expired - Lifetime US3000736A (en) | 1958-03-31 | 1958-03-31 | Photographic silver halide diffusion transfer process |
Country Status (5)
Country | Link |
---|---|
US (1) | US3000736A (fr) |
BE (1) | BE577129A (fr) |
DE (1) | DE1064807B (fr) |
FR (1) | FR1221438A (fr) |
GB (1) | GB907146A (fr) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3261682A (en) * | 1962-09-29 | 1966-07-19 | Siemens Ag | Zirconium alloys containing cerium and yttrium |
US3311473A (en) * | 1962-06-28 | 1967-03-28 | Eastman Kodak Co | Silver halide diffusion process and products therefor |
US3607269A (en) * | 1968-04-01 | 1971-09-21 | Polaroid Corp | Image-receiving elements and photographic processes employing same |
US3775122A (en) * | 1967-07-28 | 1973-11-27 | American Can Co | Image production using photosensitive compositions of nitrone which is heat developed |
US4172728A (en) * | 1977-12-16 | 1979-10-30 | E. I. Du Pont De Nemours And Company | High contrast continuous tone developer and process of use |
US4298673A (en) * | 1972-03-10 | 1981-11-03 | Fuji Photo Film Co., Ltd. | Lithographic type diffusion transfer developing composition |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3099209A (en) * | 1960-02-26 | 1963-07-30 | Eastman Kodak Co | Process of treating residual positive silver halide images with organic sulfur to render said images oleophilic |
NL259197A (fr) * | 1960-12-17 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2496940A (en) * | 1948-10-21 | 1950-02-07 | Eastman Kodak Co | Mixed grain photographic process |
US2497917A (en) * | 1947-10-17 | 1950-02-21 | Eastman Kodak Co | Method of producing direct positive photographs having increased density |
US2704721A (en) * | 1954-04-22 | 1955-03-22 | Polaroid Corp | Photographic diffusion transfer reversal processes |
-
0
- BE BE577129D patent/BE577129A/xx unknown
-
1958
- 1958-03-31 US US724815A patent/US3000736A/en not_active Expired - Lifetime
-
1959
- 1959-01-22 DE DEE17040A patent/DE1064807B/de active Pending
- 1959-03-26 GB GB10504/59A patent/GB907146A/en not_active Expired
- 1959-03-27 FR FR790623A patent/FR1221438A/fr not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2497917A (en) * | 1947-10-17 | 1950-02-21 | Eastman Kodak Co | Method of producing direct positive photographs having increased density |
US2496940A (en) * | 1948-10-21 | 1950-02-07 | Eastman Kodak Co | Mixed grain photographic process |
US2704721A (en) * | 1954-04-22 | 1955-03-22 | Polaroid Corp | Photographic diffusion transfer reversal processes |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3311473A (en) * | 1962-06-28 | 1967-03-28 | Eastman Kodak Co | Silver halide diffusion process and products therefor |
US3261682A (en) * | 1962-09-29 | 1966-07-19 | Siemens Ag | Zirconium alloys containing cerium and yttrium |
US3775122A (en) * | 1967-07-28 | 1973-11-27 | American Can Co | Image production using photosensitive compositions of nitrone which is heat developed |
US3607269A (en) * | 1968-04-01 | 1971-09-21 | Polaroid Corp | Image-receiving elements and photographic processes employing same |
US4298673A (en) * | 1972-03-10 | 1981-11-03 | Fuji Photo Film Co., Ltd. | Lithographic type diffusion transfer developing composition |
US4172728A (en) * | 1977-12-16 | 1979-10-30 | E. I. Du Pont De Nemours And Company | High contrast continuous tone developer and process of use |
Also Published As
Publication number | Publication date |
---|---|
GB907146A (en) | 1962-10-03 |
BE577129A (fr) | |
DE1064807B (de) | 1959-09-03 |
FR1221438A (fr) | 1960-06-01 |
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