US3021212A - Developers for photographic reversal processes - Google Patents
Developers for photographic reversal processes Download PDFInfo
- Publication number
- US3021212A US3021212A US833685A US83368559A US3021212A US 3021212 A US3021212 A US 3021212A US 833685 A US833685 A US 833685A US 83368559 A US83368559 A US 83368559A US 3021212 A US3021212 A US 3021212A
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- United States
- Prior art keywords
- pyrazolidone
- photographic
- selenocyanide
- silver halide
- sodium
- 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
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- 238000000034 method Methods 0.000 title claims description 16
- 230000008569 process Effects 0.000 title description 8
- -1 SILVER HALIDE Chemical class 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- 239000000839 emulsion Substances 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 150000001340 alkali metals Chemical class 0.000 claims description 19
- 239000012670 alkaline solution Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000011161 development Methods 0.000 claims description 5
- 230000001603 reducing effect Effects 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000203 mixture Substances 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WTKUDAMSULHEKV-UHFFFAOYSA-N [Se](C#N)C#N.[K] Chemical compound [Se](C#N)C#N.[K] WTKUDAMSULHEKV-UHFFFAOYSA-N 0.000 description 7
- YTCRRZPPDGMMBV-UHFFFAOYSA-N sodium;isoselenocyanate Chemical compound [Na+].[N-]=C=[Se] YTCRRZPPDGMMBV-UHFFFAOYSA-N 0.000 description 7
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 6
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium erythorbate Chemical compound [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 5
- 235000010352 sodium erythorbate Nutrition 0.000 description 5
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- FJWJYHHBUMICTP-UHFFFAOYSA-N 4,4-dimethylpyrazolidin-3-one Chemical compound CC1(C)CNNC1=O FJWJYHHBUMICTP-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- SVJPLZNMCJQWPJ-UHFFFAOYSA-N 1-(4-methylphenyl)pyrazolidin-3-one Chemical compound C1=CC(C)=CC=C1N1NC(=O)CC1 SVJPLZNMCJQWPJ-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FZQDYEPVHITTBB-UHFFFAOYSA-N Cl[Br][I][Ag] Chemical compound Cl[Br][I][Ag] FZQDYEPVHITTBB-UHFFFAOYSA-N 0.000 description 1
- RGJNDCGKVVCZBE-UHFFFAOYSA-N O=C1CCN(N1)C1=CC=C(C=C1)C#N Chemical compound O=C1CCN(N1)C1=CC=C(C=C1)C#N RGJNDCGKVVCZBE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003289 ascorbyl group Chemical class [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YERGVOHOBQDWPR-UHFFFAOYSA-N n-[4-(4,4-diethyl-3-oxopyrazolidin-1-yl)phenyl]acetamide Chemical compound N1C(=O)C(CC)(CC)CN1C1=CC=C(NC(C)=O)C=C1 YERGVOHOBQDWPR-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 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
- G03C5/50—Reversal development; Contact processes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
- G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
- G01J5/20—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using resistors, thermistors or semiconductors sensitive to radiation, e.g. photoconductive devices
Definitions
- the present invention relates to improved developers for producing direct positive images, and more particularly relates to a method of utilizing such developers to produce direct positive images by a reversal technique utilizing only one treating bath in order to obtain reversal.
- reversal development is an involved process and involves no fewer than five essential operations: development of the latent image, bleaching and clearing to remove the developed negative silver image, exposing the remaining silver halide to light, and finally, reducing the silver halide to metallic silver in order to form the reversal image.
- operaL'ons including rinsing, hardening, fixing and washing treatments.
- photographic developing baths which produce a direct positive image without necessitating elaborate processing techniques and without the necessity for multiple treatments in rinsing baths, fixing baths, etc.
- an object of my invention to provide new photographic developers for obtaining in a single step positive black-and-white images. Another object is to provide a method for using such photographic developing baths. Still another object is to provide photographic developing baths which produce positive images in a one-bath reversal process. Other objects will become apparent from a consideration of the following description and examples.
- new photographic developing solutions which contain an alkali metal selenocyanide.
- These salts can be represented by the following general formula:
- MSeCN wherein M represents an alkali metal, such as sodium, potassium, etc.
- Example 1 Ordinary X-ray film comprising a photographic silver bromiodide emulsion coated on cellulose acetate support was exposed in the normal manner to light of the type minutes at 68 F. in a solution having the following composition:
- a medium-to-fine grain positive silver bromiodide emulsion of low gelatin content was exposed in the normal manner and then processed for 5 to 20 seconds at 95 F. in a solution having the following composition:
- Example 3 A fine-grain, slow, cine-positive photographic gelatinosilver-bromiodide emulsion was coated on a conventional cellulose acetate support and exposed in the normal manner. This film was then developed for 20 seconds at 95 F. in a solution having the following composition:
- the phenidone developer in the above developing composition can be replaced by an equivalent amount of Elon-developer, although somewhat increased silvering of the emulsion is produced by this change.
- Example 4 Another sample of the silver bromiodide emulsion described in Example 3 was processed in the developer shown in that example, except that 4 cos. of monothioglycerol were added to the developer. Addition of this material caused an increase in the maximum density with no apparent change in the image tone.
- Example 5 A fine-grain, slow, cine-positive photographic gelatinosilver-brorniodide emulsion was coated on a conventional cellulose acetate support and exposed in the normal manner. The exposed film was then'develop'ed for 20 seconds at 95 F. in a solution having the following composition:
- Phenidone developer .grarns 10.0 Sodium isoascorbate do 40.0 Sodium hydroxide do 30.0 Potassium selenocyanide do 40.0 5,;8-Dithiasuberic acid do 40.0 Monothioglycerol ml 5.0
- a reversed image having a black or blue-black tone was produced.
- the alkali metal selenocyanides used in my invention have a rather marked solvent effect on the silver halides and thus make it possible to use the developers of my invention to obtain direct positive images by the dilfusion transfer process.
- the following example will serve to illustrate this technique as applied to my new photographic developers.
- Example 6 A photographic film comprising a silver bromiodide negative emulsion coated on a cellulose acetate support was exposed in the normal manner and bathed for 6 seconds at room temperature in a solution having the following composition:
- alkali metal selenocyanide in photographic developers has been observed to occur in a variety of developers designed for use in black-and-white photography.
- These developers can comprise conventional blackand-White developers 7 including polyhydroxybenzenes (e.g., hydroquinone, chlorohydroquinone, alkylsubstituted hydroquinones, etc.), p-aminophenols, B-pyrazolidone, etc.
- S-pyrazolidones useful in the photographic developers of my invention include those described in Kendall US. Patent 2,289,367, issued July 14, 1942; Reynolds et al. US. Patent 2,743,279, issued April 24, 1956, and Allen et al. U.S. Patent 2,772,282, issued November 27, 1956, for example.
- Typical 3-pyrazolidone described by the patents include:
- the activity of the alkali metal selenocyanides useful in my invention can be varied by suitable alteration of the pH of the developing solutions. Particularly useful results have been obtained when the pH of the solution is above about 9.0. Especially useful results have been obtained at a pH of about 9.8 or higher.
- Alkaline materials suitable for use in adiusting the pH of the developing solutions are sodium hydroxide,'potasslum hydroxide, sodium carbonate, etc.
- novel developers of my invention can be used to obtain reversed images in treating many of the common photographic gelatino-silver-halide developing-out emulsions. While many of the previous methods of producmg reversal by a chemical means require the use of extremely slow, fine-grain emulsions, it can be seen from the above examples that my invention provides reversed nnages even with high-speed negative bromiodide emulsions.
- the silver halides of the photographic emulsions useful in practicing my invention can be varied and include not only the silver bromiodide emulsions illustrated in the above examples but emulsions comprising other silver halides, such as silver bromide, silver chlorobromide, silve bromiodide, silver chlorobromiodide, etc.
- Development times can vary depending upon the particular emulsion being developed, concentration of ingredients in the developer, etc.
- concentration of ingredients in the developer etc.
- the most advantageous time for a given emulsion can be determined by running a series of test strips wherein the only variable in the process is the developing time.
- the optimum concentration of ingredients for a given developer can be determined by variation of the concentration of only one of the ingredients in a given series of tests. Such matters are well understood by those skilled in the art.
- a suitable fixing paper can be made by precipitating sodium thioglyceride from a solution containing one mole of a-monothioglycerol and one mole of sodium hydroxide.
- a paper base which may be coated with a colloid layer, such as gelatin, carboxymethyl cellulose, etc., is then soaked for 30 seconds in a solution of a sodium thioglyceride and then air dried.
- the fixing paper can then be processed in contact with the photographic material with a sufficient amount of liquid between the two surfaces.
- This liquid can come solely from the developed photographic material and/ or from the wetted fixing paper.
- the fixing agent can be a different mercapto compound, such as thiobarbituric acid, ora sodium salt thereof.
- a photographic developer for producing direct positive images comprising an alkaline solution of an organic silver halide developing agent for producing black-andwhite images and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
- a photographic developer for producing direct positive images comprising an alkaline solution of a polyhydroxybenzene silver halide developing agent and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
- a photographic developer for producing direct positive images comprising an alkaline solution of a 3-pyrazolidone silver halide developer and fro-m about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
- a photographic developer for producing direct positive images comprising an alkaline solution of a 3-pyrazolidone-silver halide developer, from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide and a water-soluble ascorbic acid salt.
- a photographic developer for producing direct positive images comprising an alkaline solution of hydroquinone and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
- a photographic developer for producing direct posi tive images comprising an alkaline solution of hydroquinone and from about 0.2 to about 50.0 grams per liter of solution of potassium selenocyanide.
- a photographic developer for producing direct positive images comprising an alkaline solution of hydroquinone and from about 0.2 to about 50.0 grams per liter of solution of sodium selenocyanide.
- a photographic developer for producing direct positive images comprising an alkaline solution of l-phenyl- 3-pyrazolidone and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
- a photographic developer for producing direct positive images comprising an alkaline solution of l-phenyl- 3-pyrazolidone and from about 0.2 to about 50.0 grams per liter of solution of potassium selenocyanide.
- a photographic developer for producing direct positive images comprising an alkaline solution of l-phenyl- 3-pyrazolidone and from about 0.2 to about 50.0 grams per liter of solution of sodium selenocyanide.
- a photographic developing solution having the following composition:
- a photographic developing solution having the following composition:
- a photographic developing solution having the following composition:
- a photographic developing solution having the following composition:
- veloping agent for reducing exposed silver halide to metallic silver, and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide, and difiusing unexposed silver halide from said exposed photographic silver halide emulsion into said receiving layer.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
United States Patent O 3,021,212 DEVELOPERS FOR PHOTOGRAPH-HG REVERSAL PROCESSES Nancy H. King, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Aug. 14-, 1959, Ser. No. 833,685 20 Ciaims. (Cl. 9629) The present invention relates to improved developers for producing direct positive images, and more particularly relates to a method of utilizing such developers to produce direct positive images by a reversal technique utilizing only one treating bath in order to obtain reversal.
Frequently, reversal development is an involved process and involves no fewer than five essential operations: development of the latent image, bleaching and clearing to remove the developed negative silver image, exposing the remaining silver halide to light, and finally, reducing the silver halide to metallic silver in order to form the reversal image. In addition, there are likely to be several other operaL'ons including rinsing, hardening, fixing and washing treatments.
On the other hand, many of the previously-described processes for producing direct positive images in a onebath reversal process by means of chemical substances result in too high a minimum density to make the use of such chemical treatment practical.
Reversal by chemical substances, such as hydrogen peroxide, sodium arsenite, sodium hypophosphite, stannous chloride, persulfates, organic peroxides and the like have previously been described. See article by Walter Clark in The Photographic Journal, vol. 64 (1954), pages 363-3 69.
According to the present invention, photographic developing baths are provided which produce a direct positive image without necessitating elaborate processing techniques and without the necessity for multiple treatments in rinsing baths, fixing baths, etc.
It is, therefore, an object of my invention to provide new photographic developers for obtaining in a single step positive black-and-white images. Another object is to provide a method for using such photographic developing baths. Still another object is to provide photographic developing baths which produce positive images in a one-bath reversal process. Other objects will become apparent from a consideration of the following description and examples.
According to the present invention, new photographic developing solutions are provided which contain an alkali metal selenocyanide. These salts can be represented by the following general formula:
MSeCN wherein M represents an alkali metal, such as sodium, potassium, etc.
The following examples will serve to illustrate briefly the new photographic developers useful in practicing my invention, and methods for using such developers.
Example 1 Ordinary X-ray film comprising a photographic silver bromiodide emulsion coated on cellulose acetate support was exposed in the normal manner to light of the type minutes at 68 F. in a solution having the following composition:
p N-methylaminophenol sulfate "grams" 2.5 Sodium sulfite (desiccated) do 30.0 Hydroquinone do 2.5 Sodium metaborate octahydrate do 10.0 Potassium bromide do 0.5 Carbitol ccs 100.0 Borax grams 10.0 Potassium selenocyanide do 2.0
Water to make 1 liter.
A medium-to-fine grain positive silver bromiodide emulsion of low gelatin content was exposed in the normal manner and then processed for 5 to 20 seconds at 95 F. in a solution having the following composition:
Grams Phenidone developer 10.0 Sodium isoascorbat 40.0 Sodium selenocyanide 20.0 Sodium hydroxide 30.0
Water to make 1 liter.
'1 1-pheny1-3-pyrazolidone.
A reversed image was obtained which was reddish in tone and it was found unnecessary to fix the image in the normal manner (fixation showed no loss of density in any area after fixation). It was also found that the reversal effect was obtained either in total darkness or by development underrsafelight conditions suitable for the product being processed.
Example 3 A fine-grain, slow, cine-positive photographic gelatinosilver-bromiodide emulsion was coated on a conventional cellulose acetate support and exposed in the normal manner. This film was then developed for 20 seconds at 95 F. in a solution having the following composition:
I Grams Phenidone developer 10.0 Sodium isoascorbate 40.0 Potassium selenocyanide 40.0 Sodium hydroxide 30.0
Water to make 1 liter.
A reddish reversal image was obtained.
The phenidone developer in the above developing composition can be replaced by an equivalent amount of Elon-developer, although somewhat increased silvering of the emulsion is produced by this change.
given by intensifying screens and then developed for 10 Example 4 Another sample of the silver bromiodide emulsion described in Example 3 was processed in the developer shown in that example, except that 4 cos. of monothioglycerol were added to the developer. Addition of this material caused an increase in the maximum density with no apparent change in the image tone.
Example 5 A fine-grain, slow, cine-positive photographic gelatinosilver-brorniodide emulsion was coated on a conventional cellulose acetate support and exposed in the normal manner. The exposed film was then'develop'ed for 20 seconds at 95 F. in a solution having the following composition:
Phenidone developer .grarns 10.0 Sodium isoascorbate do 40.0 Sodium hydroxide do 30.0 Potassium selenocyanide do 40.0 5,;8-Dithiasuberic acid do 40.0 Monothioglycerol ml 5.0
Water to make 1.0 liter.
A reversed image having a black or blue-black tone was produced.
Omission of the monothioglycerol from the developing composition of Example 5 caused a marked decrease in the reversal effect as a result of the presence of the dithiasuberic acid. However, addition of the monothioglycerol provided a convenient means of controlling the reversal of the selenocyanide, and overcoming the undesired effects at the dithiasuberic acid.
The alkali metal selenocyanides used in my invention have a rather marked solvent effect on the silver halides and thus make it possible to use the developers of my invention to obtain direct positive images by the dilfusion transfer process. The following example will serve to illustrate this technique as applied to my new photographic developers.
Example 6 A photographic film comprising a silver bromiodide negative emulsion coated on a cellulose acetate support was exposed in the normal manner and bathed for 6 seconds at room temperature in a solution having the following composition:
Grams Hydroquinone 35 Sodium sulfit i 80 Sodium .selenocyanide 28;
Sodium hydroxide Water to make 1.0 liter.
Immediately after bathing the'film was rolled in intimate contact with a paper receiving sheet nucleated with lead sulfide. After contact for 2 minutes, the film was stripped from the receiving sheet, leaving a positive image having high maximum density and adequate scale on the receiving sheet. The results were equivalent to those produced with the same materials and a similar developer containing about 15 grams/liter of sodium thiosulfate instead of sodium selenocyanide. Use of lower concentrations of sodium selenocyanide caused commensurate loss in the density of the positive images, although this was compensated for by using silver bromiodide negatives of higher speed.
The exact mechanism leading to the formation of direct positive images by application of the novel photographic developers of my invention is not completely understood. However, it is believed that the order of events is somewhat similar to that of a monobath in the areas which have received the highest exposures developed in a normal manner. For this reason, it may be desirable to slightly underexpose the original light-sensitive material. The unexposed areas or areas of very low exposure are seen to become transparent, and at this point the similarity to mcnobaths no longer holds. Further processing causes a gradual reduction in the transparency of the cleared areas until these areas transmit substantially less light than the exposed areas. The difference in density between the unexposed areas and the exposed areas may be as much as 6.0 or more.
The effect of the alkali metal selenocyanide in photographic developers has been observed to occur in a variety of developers designed for use in black-and-white photography. These developers can comprise conventional blackand-White developers 7 including polyhydroxybenzenes (e.g., hydroquinone, chlorohydroquinone, alkylsubstituted hydroquinones, etc.), p-aminophenols, B-pyrazolidone, etc. S-pyrazolidones useful in the photographic developers of my invention include those described in Kendall US. Patent 2,289,367, issued July 14, 1942; Reynolds et al. US. Patent 2,743,279, issued April 24, 1956, and Allen et al. U.S. Patent 2,772,282, issued November 27, 1956, for example. Typical 3-pyrazolidone described by the patents include:
1-phenyl-3 -pyrazolidone 1-m-nitrophenyl-3-pyrazolidone 1-p-nitrophenyl-3 -pyrazolidone l-p-chlorophenyl-3 -pyrazolidone 1-p-cyanophenyl-3 -pyrazolidone l-p-fl-methanesulfonamidoethylphenyl-3-pyrazolidone 1p-B-hydroxyethylphenyl-Ii-pyrazolidone 1- p-carboxymethylphenyl) -3 -pyrazolidone 1-p-tolyl-3 -pyrazolidone l-o-tolyl-3-pyrazolidone l-m-tolyl-3-pyrazolidone 1- 2-b enzothiazolyl) -3-pyrazolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone 1-p-aminophenyl-4-methyl-4-propyl-3 -pyrazolidone l-p-chlorophenyl-4-methy1-4-ethyl-3-pyrazolidone 1-p-acetamidophenyl-4,4-diethyl-3 -pyrazolidone l-p-B-hydroxyethylphenyl-4,4-dimethyl-B-pyrazolidone l-p-hydroxyphenyl-4,4-dimethyl-3 -pyrazolid one 1-p-methoxyphenyl-4,4-diethyl-3-pyrazolidone 1-p-tolyl-4,4-dimethyl-3-pyrazolidone '1- (7 -hydroxy-2-naphthyl) -4-methyl-4-n-propyl'3- pyrazolidone 1-p-nitrophenyl-4,4-dimethyl-3 -pyrazolidone 1-p-cyanophenyl-4,4-dimethyl-3-pyrazolidone 1-p acetylaminophenyl-4,4-dimethyl-3-pyrazolidone 1-p-benzylphenyl-4,4-dimethyl-3-pyrazolidone 1-methyl-4,4-dimethyl-3-pyrazolidone 1-p-carboxyphenyl-4,4-dimethyl-3 -pyrazolidone 1-carboxymethyl-4,4-dimethyl-3pyrazolidone 1-hydroxyethyl-4,4-dimethyl-3-pyrazolidone l-m-aminophenyl-4,4-dimethyl-3 -pyrazolidone 1-m-chlorophenyl-4-methyl-4-ethyl- 3-pyrazolidone 1-m-acetamidophenyl-4,4-diethyl- 3 -pyrazoli done The concentration of the alkali metal selenocyanide useful in my invention can be varied, depending upon the particular silver halide emulsion being processed, the concentration of silver halide in the emulsion, the pH of the developer, the nature and concentration of the developing agents, the presence or absence of stabilizers, such as sodium sulfite, sodium isoascorbate, etc., and the presonce or absence of toning materials, such as ,B,B'-dithiasuberic acid and monothioglycerol. In general, I have found that quite useful results can be obtained wherein the concentration of the alkali metal selenocyanides vary from about 0.2 to about 50.0 grams per liter of solution.
The activity of the alkali metal selenocyanides useful in my invention can be varied by suitable alteration of the pH of the developing solutions. Particularly useful results have been obtained when the pH of the solution is above about 9.0. Especially useful results have been obtained at a pH of about 9.8 or higher.
Alkaline materials suitable for use in adiusting the pH of the developing solutions are sodium hydroxide,'potasslum hydroxide, sodium carbonate, etc.
The novel developers of my invention can be used to obtain reversed images in treating many of the common photographic gelatino-silver-halide developing-out emulsions. While many of the previous methods of producmg reversal by a chemical means require the use of extremely slow, fine-grain emulsions, it can be seen from the above examples that my invention provides reversed nnages even with high-speed negative bromiodide emulsions. The silver halides of the photographic emulsions useful in practicing my invention can be varied and include not only the silver bromiodide emulsions illustrated in the above examples but emulsions comprising other silver halides, such as silver bromide, silver chlorobromide, silve bromiodide, silver chlorobromiodide, etc.
Development times can vary depending upon the particular emulsion being developed, concentration of ingredients in the developer, etc. The most advantageous time for a given emulsion can be determined by running a series of test strips wherein the only variable in the process is the developing time. Similarly the optimum concentration of ingredients for a given developer can be determined by variation of the concentration of only one of the ingredients in a given series of tests. Such matters are well understood by those skilled in the art.
As indicated above, it is generally unnecessary to stabilize or fix the photographic images produced according to the present invention. However, where it is desirable to fix or stabilize the photographic image, it has been found that this can conveniently be done by merely contacting the processed photographic material with a Web or stabilizing paper having a coating thereon containing the fixing or stabilizing ingredient. For instance, a suitable fixing paper can be made by precipitating sodium thioglyceride from a solution containing one mole of a-monothioglycerol and one mole of sodium hydroxide. A paper base, which may be coated with a colloid layer, such as gelatin, carboxymethyl cellulose, etc., is then soaked for 30 seconds in a solution of a sodium thioglyceride and then air dried. The fixing paper can then be processed in contact with the photographic material with a sufficient amount of liquid between the two surfaces. This liquid can come solely from the developed photographic material and/ or from the wetted fixing paper. Alternatively, the fixing agent can be a different mercapto compound, such as thiobarbituric acid, ora sodium salt thereof.
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 eifected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
What I claim as my invention and desire secured by Letters Patent of the United States is:
1. A photographic developer for producing direct positive images comprising an alkaline solution of an organic silver halide developing agent for producing black-andwhite images and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
2. A photographic developer for producing direct positive images comprising an alkaline solution of a polyhydroxybenzene silver halide developing agent and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
3. A photographic developer as defined in claim 2 wherein the alkali metal selenocyanide is potassium selenocyanide.
4. A photographic developer as defined in claim 2 wherein the alkali metal selenocyanide is sodium selenocyanide.
5. A photographic developer for producing direct positive images comprising an alkaline solution of a 3-pyrazolidone silver halide developer and fro-m about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
6. A photographic developer for producing direct positive images comprising an alkaline solution of a 3-pyrazolidone-silver halide developer, from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide and a water-soluble ascorbic acid salt.
7. A. photographic developer as defined in claim 5 wherein the alkali metal selenocyanide is potassium selenocyanide.
8. A photographic developer as defined in claim 5 wherein the alkali metal selenocyanide is sodium selenocyanide.
9. A photographic developer for producing direct positive images comprising an alkaline solution of hydroquinone and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
10. A photographic developer for producing direct posi tive images comprising an alkaline solution of hydroquinone and from about 0.2 to about 50.0 grams per liter of solution of potassium selenocyanide.
11. A photographic developer for producing direct positive images comprising an alkaline solution of hydroquinone and from about 0.2 to about 50.0 grams per liter of solution of sodium selenocyanide.
12. A photographic developer for producing direct positive images comprising an alkaline solution of l-phenyl- 3-pyrazolidone and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide.
13. A photographic developer for producing direct positive images comprising an alkaline solution of l-phenyl- 3-pyrazolidone and from about 0.2 to about 50.0 grams per liter of solution of potassium selenocyanide.
14. A photographic developer for producing direct positive images comprising an alkaline solution of l-phenyl- 3-pyrazolidone and from about 0.2 to about 50.0 grams per liter of solution of sodium selenocyanide.
15. A photographic developing solution having the following composition:
Water to make 1 liter.
16. A photographic developing solution having the following composition:
Grams 1-phenyl-3-pyrazolidone 10.0 Sodium isoascorbate 40.0 Sodium selenocyanid 20.0 Sodium hydroxide 30.0
Water to make 1 liter.
17. A photographic developing solution having the following composition:
Grams 1-phenyl-3-pyrazolidone 10.0 Sodium isoascorbate 40.0 Potassium selenocyanide 400 Sodium hydroxide 30.0
Water to make 1 liter.
18. A photographic developing solution having the following composition:
1-phenyl-3-pyrazolidone grams 10.0 Sodium isoascorbate do 40.0 Potassium selenocyanide do 40.0 Sodium hydroxide do 30.0 Monothioglycerol ccs 4.0
Water to make 1 liter.
19. A photographic developing solution having the fol lowing composition:
l-pheny1-3-pyrazolidone grams 10.0 Sodium isoascorbate do 40.0 Sodium hydroxide do 300 Potassium selenocyanide do 40.0 pfi dithiasuberic acid do.... 40.0 Monothioglycerol ml 5.0
Water to make 1.0 liter.
veloping agent for reducing exposed silver halide to metallic silver, and from about 0.2 to about 50.0 grams per liter of solution of an alkali metal selenocyanide, and difiusing unexposed silver halide from said exposed photographic silver halide emulsion into said receiving layer.
References Cited in the file of this patent UNITED STATES PATENTS 1,623,499 Sheppard Apr. 5, 1927 2,698,245 Land V Dec. 28, 1954 2,740,717 Yutzy Apr. 3, 1956 OTHER REFERENCES Chemical Abstracts, 34, 2281. Chemical Abstracts, 31, 5717.
Claims (1)
- 20. A METHOD OF PRODUCING DIRECT POSITIVE IMAGES COMPRISING DEVELOPING AN EXPOSED PHOTOGRAPHIC SILVER HALIDE EMULSION IN CONTACT WITH A RECEIVING LAYER CONTAINING SILVER PRECIPITATING MATERIAL FOR UNEXPOSED SILVER HALIDE, SAID DEVELOPMENT BEING CARRIED OUT IN THE PRESENCE OF AN ALKALINE SOLUTION COMPRISING AN ORGANIC SILVER HALIDE DEVELOPING AGENT FOR REDUCING EXPOSED SILVER HALIDE TO METALLIC SILVER, AND FROM ABOUT 0.2 TO ABOUT 50.0 GRAMS PER LITER OF SOLUTION OF AN ALKALI METAL SELENOCYANIDE, AND DIFFUSING UNEXPOSED SILVER HALIDE FROM SAID EXPOSED PHOTOGRAPHIC SILVER HALIDE EMULSION INTO SAID RECEIVING LAYER.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE593938D BE593938A (en) | 1959-08-14 | ||
US833685A US3021212A (en) | 1959-08-14 | 1959-08-14 | Developers for photographic reversal processes |
FR834443A FR1277988A (en) | 1959-08-14 | 1960-08-09 | New photographic developer and process using this developer |
GB27985/60A GB956368A (en) | 1959-08-14 | 1960-08-12 | Improved photographic developers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US833685A US3021212A (en) | 1959-08-14 | 1959-08-14 | Developers for photographic reversal processes |
Publications (1)
Publication Number | Publication Date |
---|---|
US3021212A true US3021212A (en) | 1962-02-13 |
Family
ID=25265016
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US833685A Expired - Lifetime US3021212A (en) | 1959-08-14 | 1959-08-14 | Developers for photographic reversal processes |
Country Status (4)
Country | Link |
---|---|
US (1) | US3021212A (en) |
BE (1) | BE593938A (en) |
FR (1) | FR1277988A (en) |
GB (1) | GB956368A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3241960A (en) * | 1961-10-24 | 1966-03-22 | American Optical Corp | Method for making vectographs |
US3295975A (en) * | 1962-09-15 | 1967-01-03 | Agfa Ag | Black-and-white developer for photographic reversal processes |
US3464822A (en) * | 1965-09-13 | 1969-09-02 | Du Pont | Process for making electrically conductive images |
US5166045A (en) * | 1989-06-19 | 1992-11-24 | Eastman Kodak Company | Doping of silver halide emulsions with group VIB compounds to form improved photoactive grains |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1623499A (en) * | 1925-06-16 | 1927-04-05 | A corpora | |
US2698245A (en) * | 1946-04-13 | 1954-12-28 | Polaroid Corp | Photographic product and process for making a positive transfer image |
US2740717A (en) * | 1952-05-03 | 1956-04-03 | Eastman Kodak Co | Photographic transfer process |
-
0
- BE BE593938D patent/BE593938A/xx unknown
-
1959
- 1959-08-14 US US833685A patent/US3021212A/en not_active Expired - Lifetime
-
1960
- 1960-08-09 FR FR834443A patent/FR1277988A/en not_active Expired
- 1960-08-12 GB GB27985/60A patent/GB956368A/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1623499A (en) * | 1925-06-16 | 1927-04-05 | A corpora | |
US2698245A (en) * | 1946-04-13 | 1954-12-28 | Polaroid Corp | Photographic product and process for making a positive transfer image |
US2740717A (en) * | 1952-05-03 | 1956-04-03 | Eastman Kodak Co | Photographic transfer process |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3241960A (en) * | 1961-10-24 | 1966-03-22 | American Optical Corp | Method for making vectographs |
US3295975A (en) * | 1962-09-15 | 1967-01-03 | Agfa Ag | Black-and-white developer for photographic reversal processes |
US3464822A (en) * | 1965-09-13 | 1969-09-02 | Du Pont | Process for making electrically conductive images |
US5166045A (en) * | 1989-06-19 | 1992-11-24 | Eastman Kodak Company | Doping of silver halide emulsions with group VIB compounds to form improved photoactive grains |
Also Published As
Publication number | Publication date |
---|---|
GB956368A (en) | 1964-04-29 |
BE593938A (en) | |
FR1277988A (en) | 1961-12-08 |
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