US3515555A - Toning composition for direct positive paper - Google Patents
Toning composition for direct positive paper Download PDFInfo
- Publication number
- US3515555A US3515555A US621460A US3515555DA US3515555A US 3515555 A US3515555 A US 3515555A US 621460 A US621460 A US 621460A US 3515555D A US3515555D A US 3515555DA US 3515555 A US3515555 A US 3515555A
- Authority
- US
- United States
- Prior art keywords
- toning
- direct positive
- composition
- tones
- alkali metal
- 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
- 239000000203 mixture Substances 0.000 title description 38
- 239000000839 emulsion Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 16
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 210000004185 liver Anatomy 0.000 description 9
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZGZUKKMFYTUYHA-HNNXBMFYSA-N (2s)-2-amino-3-(4-phenylmethoxyphenyl)propane-1-thiol Chemical compound C1=CC(C[C@@H](CS)N)=CC=C1OCC1=CC=CC=C1 ZGZUKKMFYTUYHA-HNNXBMFYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- -1 silver halide Chemical class 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- ZLCCLBKPLLUIJC-UHFFFAOYSA-L disodium tetrasulfane-1,4-diide Chemical compound [Na+].[Na+].[S-]SS[S-] ZLCCLBKPLLUIJC-UHFFFAOYSA-L 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 208000012641 Pigmentation disease Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MWCGLTCRJJFXKR-UHFFFAOYSA-N n-phenylethanethioamide Chemical compound CC(=S)NC1=CC=CC=C1 MWCGLTCRJJFXKR-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/40—Chemically transforming developed images
- G03C5/46—Toning
Definitions
- This invention relates to novel compositions useful for toning developed images of direct positive photographic emulsions and, particularly, to the use of the novel compositions for producing brown tones on direct positive photographic emulsions after exposure and development thereof, which emulsions normally produce a black and white image. More particularly, the invention is directed to the production of warm brown tones on direct positive photographic emulsions by treating such emulsions after development with a toning composition comprising an inorganic sulfur-containing compound, an alkali metal hydroxide, a thioamine or derivative thereof and an alkali metal iodide.
- photographic images can be produced on silver halide direct positive emulsions by methods in which the exposed emulsion is chemically modified to produce a direct positive image.
- the normal processing of direct positive photographic emulsions comprises developing the film, bleaching the developed image, clearing and neutralizing the bleached image, re-exposing the emulsion and then redeveloping the image in the original developer.
- This process produces a black and White print which is useful for most purposes but which is disadvantageous in certain respects.
- a further object of the invention is the provision of a method of toning silver bromide direct positive emulsions which normally produce only black and white tones, which comprises treating such emulsions with the novel toning compositions of this invention whereby brown tones are obtained.
- the present invention provides novel toning compositions for direct positive papers comprising an inorganic sulfurcontaining compound, an alkali metal hydroxide, a thioamine or derivative thereof and an alkali metal iodide. It has unexpectedly been found that the novel toning composition of this invention produces a result dilferent than that obtained with the similar known toners containing thiourea and sodium hydroxide or odium sulfide. Thus, the toning activity of the combination of the components comprising the composition of the present invention behaves dilferently than would be expected from the activity of the individual compounds therein.
- the direct positive photographic paper with which the toning composition of the invention is used, is a silver bromide gelatin emulsion on a paper base (e.g. Super Speed Direct Positive Paper, Type 1703 sold by the Eastman Kodak Co).
- a paper base e.g. Super Speed Direct Positive Paper, Type 1703 sold by the Eastman Kodak Co.
- Such a paper after normal exposure, development, bleaching, clearing, re-exposure and re-developing in the original developer, produces a black and white print.
- the toning composition of the present invention comprises (1) an inorganic sulfur-containing compound, (2) an alkali metal hydroxide or alkali metal compound which will react in solution to produce the hydroxide, (3) a thioamine or derivatives thereof and (4) an alkali metal iodide.
- liver of sulfur is preferably utilized as the inorganic sulfur-containing compound in the toning composition of the invention, an appropriate amount of sodium tetrasulfide solution may be utilized in lieu thereof.
- Liver of sulfur is prepared by the fusion of potassium carbonate and sulfur and contains chiefly a mixture of potassium sulfide and polysulfides. Not less than about 12.8% sulfur as sulfi-de is present.
- the inorganic sulfurcontaining compound or mixture is present in an amount of from about 2 g./l. to about g./l. of solution.
- thi first component is present in an amount of from about 5 to 10 g./l. of solution.
- the second component eg an alkali metal hydroxide, utilized in the composition of the invention is preferably sodium hydroxide or potassium hydroxide although other alkali metal hydroxides or alkaline compounds which will react to yield such alkali metal hydroxides, such as trisodium phosphate may be used in lieu thereof.
- This component is present in a concentration of from about 1.0 g./l. to 70 g./l. but is preferably present in the range of from about 5.0 to 10.0 g./l.
- the third component of the toning composition is a thioamine such as thiourea, acetyl thiourea, alkyl thiourea or a derivative thereof, such as appropriate amounts of thiamides, e.g. thioacetamide, thioacetanilide and the like.
- This component is preferably present in an amount of from about 0.5 g./l. to about 15 g./l. but high and lower concentrations may be utilized. Thus, a concentration of from about 1.0 to 1.5 g./l. produces beneficial results.
- the fourth component of the composition of the invention is an alkali metal iodide such as sodium iodide, potassium iodide or the like in a concentration of from about 1.0 to 15 g./l. Best results are, however, obtained in the range of about 2.0 to 3.0 g./l.
- the toning composition of the invention is useful at temperatures of from about 55 to 90 F., although 75 F. is considered to produce the most beneficial results.
- EXAMPLE 1 One liter of a concentrated toning composition of the invention is prepared by dissolving 250 g. liver of sulfur, 200 g. sodium hydroxide, 40 g. thiourea and 80 g. potassium iodide in approximately 816 g. distilled water.
- the composition has a specific gravity, at 70 F. of approximately 1.386.
- the concentrate is diluted with distilled water in a ratio of approximately 1 part concentrate to about 30 parts water. Good results will also be obtained using much more concentrated solutions.
- EXAMPLE 2 A gelatin-based, direct positive, silver bromide photographic emulsion (Kodak Type 1703) is coated onto a paper support and dried. The emulsion of the coated support thus produced is exposed to light or other activating radiation of suitable intensity for forming a latent image on the emulsion and the emulsion is then developed, rinsed and then bleached in a dichromate/sulfuric acid bath. After bleaching, the emulsion is rinsed and cleared in a sodium bisulfite/sodium sulfite solution and re-developed using a conventional 2% sodium sulfide redeveloper. The direct positive print thus produced is toned in gradations of black and white.
- EXAMPLE 3 The silver bromide emulsion described in Example 2 is exposed to light in order to form a latent image and then developed as set forth in Example 2, substituting for the sodium sulfide re-developer used therein the composition described in Example 1.
- the positive print formed is characterized by pleasing reddish-brown tones.
- EXAMPLE 4 The direct positive emulsion of Example 2 is exposed and re-developed utilizing an aqueous toning solution containing 8.0 g./l. liver of sulfur and 6.5 g./l. sodium hydroxide. The positive print is characterized by a neutral black tone.
- EXAMPLE 5 The emulsion of Example 2 is exposed and re-developed utilizing an aqueous toning solution containing 8 g./l. liver of sulfur. The positive print is characterized by unpleasant tones of red-brown and yellow-brown.
- EXAMPLE 6 A toning solution is prepared as described in Example 1, substituting sodium tetrasulfide for liver of sulfur.
- EXAMPLE 7 A toning solution is prepared as described in Example 1, substituting thioacetamide for thiourea. Exposure and processing of Kodak Type 1703 Direct Positive Paper with this composition produces the desired image tones of a warm, brownish hue.
- EXAMPLE 8 A direct positive, silver bromide emulsion coated on a paper base (Kodak Type 1703) was developed for 60 seconds in an MQ developer at 70 F., rinsed in Water for 15 seconds, bleached for 30 seconds, rinsed again for 15 seconds, cleared for 30 seconds and again rinsed in water for 30 seconds. Redevelopment with conventional sodium sulfide re-developer gave warm black tones throughout the image.
- EXAMPLE 9 Upon substituting the composition of Example 1 in the re-development process illustrated in Example 8, the direct positive paper produced the desired warm reddish-brown tones of even density throughout the image.
- the present invention contemplates the use of other well-known photographic coating support materials such as films of cellulose esters, vinyl polymers, polyamides and halogenated olefinic polymers as well as metal film supports, textiles and glass plates.
- a toning composition for direct positive silver bromide photographic paper which comprises:
- an alkali metal sulfide (b) a substance selected from the group consisting of an alkali metal hydroxide or an alkali metal salt which will produce a hydroxide upon hydrolysis (c) a thioamide, including for example: thiourea,
- acetyl thiourea alkyl thiourea, or a derivative thereof (d) an alkali metal iodide
- a toning solution for direct positive silver bromide photographic paper consisting essentially of the following components dissolved in water:
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62146067A | 1967-03-08 | 1967-03-08 | |
| US62147167A | 1967-03-08 | 1967-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3515555A true US3515555A (en) | 1970-06-02 |
Family
ID=27088967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US621460A Expired - Lifetime US3515555A (en) | 1967-03-08 | 1967-03-08 | Toning composition for direct positive paper |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3515555A (enrdf_load_stackoverflow) |
| BE (1) | BE711839A (enrdf_load_stackoverflow) |
| DE (1) | DE1622927A1 (enrdf_load_stackoverflow) |
| FR (1) | FR1559273A (enrdf_load_stackoverflow) |
| GB (1) | GB1216243A (enrdf_load_stackoverflow) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4700368A (en) * | 1984-12-21 | 1987-10-13 | De La Rue Systems Limited | Method and apparatus for sensing sheets |
| US4965177A (en) * | 1989-08-02 | 1990-10-23 | Eastman Kodak Company | Activator solution with cold image tone-providing agent |
| US5037727A (en) * | 1989-08-02 | 1991-08-06 | Eastman Kodak Company | Activator solution with cold image tone-providing agent |
| US5100769A (en) * | 1989-05-05 | 1992-03-31 | Felix Schoeller Jr. Gmbh & Co. Kg | Paper support for light-sensitive materials with an anti-curl layer on the backside |
| US5283157A (en) * | 1993-03-22 | 1994-02-01 | Minnesota Mining And Manufacturing Company | Diffusion transfer printing plate |
| US6261747B1 (en) | 2000-05-23 | 2001-07-17 | Eastman Kodak Company | Black-and-white sepia toning kit and method for its use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2678886A (en) * | 1953-04-28 | 1954-05-18 | Ficker Vera | Production of photographs in golden tones and compositions thereof |
| US3004850A (en) * | 1958-11-28 | 1961-10-17 | Ilford Ltd | Production of positive photographic records |
| US3048486A (en) * | 1960-02-01 | 1962-08-07 | Peerless Photo Products Inc | Photographic positive printing system |
-
1967
- 1967-03-08 US US621460A patent/US3515555A/en not_active Expired - Lifetime
-
1968
- 1968-03-06 DE DE19681622927 patent/DE1622927A1/de active Pending
- 1968-03-07 GB GB01014/68A patent/GB1216243A/en not_active Expired
- 1968-03-07 BE BE711839D patent/BE711839A/xx unknown
- 1968-03-08 FR FR1559273D patent/FR1559273A/fr not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2678886A (en) * | 1953-04-28 | 1954-05-18 | Ficker Vera | Production of photographs in golden tones and compositions thereof |
| US3004850A (en) * | 1958-11-28 | 1961-10-17 | Ilford Ltd | Production of positive photographic records |
| US3048486A (en) * | 1960-02-01 | 1962-08-07 | Peerless Photo Products Inc | Photographic positive printing system |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4700368A (en) * | 1984-12-21 | 1987-10-13 | De La Rue Systems Limited | Method and apparatus for sensing sheets |
| US5100769A (en) * | 1989-05-05 | 1992-03-31 | Felix Schoeller Jr. Gmbh & Co. Kg | Paper support for light-sensitive materials with an anti-curl layer on the backside |
| US4965177A (en) * | 1989-08-02 | 1990-10-23 | Eastman Kodak Company | Activator solution with cold image tone-providing agent |
| US5037727A (en) * | 1989-08-02 | 1991-08-06 | Eastman Kodak Company | Activator solution with cold image tone-providing agent |
| US5283157A (en) * | 1993-03-22 | 1994-02-01 | Minnesota Mining And Manufacturing Company | Diffusion transfer printing plate |
| US6261747B1 (en) | 2000-05-23 | 2001-07-17 | Eastman Kodak Company | Black-and-white sepia toning kit and method for its use |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1559273A (enrdf_load_stackoverflow) | 1969-03-07 |
| BE711839A (enrdf_load_stackoverflow) | 1968-07-15 |
| GB1216243A (en) | 1970-12-16 |
| DE1622927A1 (de) | 1970-12-17 |
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