US3563746A - Use of boranocarbonates in a photographic reversal process - Google Patents
Use of boranocarbonates in a photographic reversal process Download PDFInfo
- Publication number
- US3563746A US3563746A US794397*A US3563746DA US3563746A US 3563746 A US3563746 A US 3563746A US 3563746D A US3563746D A US 3563746DA US 3563746 A US3563746 A US 3563746A
- Authority
- US
- United States
- Prior art keywords
- photographic
- colour
- potassium
- developer
- reversal
- 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
- 238000000034 method Methods 0.000 title abstract description 33
- 238000011161 development Methods 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 description 23
- 229910052709 silver Inorganic materials 0.000 description 19
- 239000004332 silver Substances 0.000 description 19
- 239000000839 emulsion Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- -1 silver halide Chemical class 0.000 description 13
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
- 238000004061 bleaching Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000975 dye Substances 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
- 239000011591 potassium Substances 0.000 description 11
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- 239000000987 azo dye Substances 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- AYLDJQABCMPYEN-UHFFFAOYSA-N (4-azaniumylphenyl)-diethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)C1=CC=C(N)C=C1 AYLDJQABCMPYEN-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
- 101100165177 Caenorhabditis elegans bath-15 gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 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
- 238000012360 testing method Methods 0.000 description 1
- FODHIQQNHOPUKH-UHFFFAOYSA-N tetrapropylene-benzenesulfonic acid Chemical compound CC1CC11C2=C3S(=O)(=O)OC(C)CC3=C3C(C)CC3=C2C1C FODHIQQNHOPUKH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000001043 yellow dye Substances 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
Definitions
- This invention relates to an improved reversal process for use in the production of positive photographic images.
- the photographic material is exposed to produce an image and is then developed in a first developer which is a conventional black-and-white developer. It is then exposed uniformly and this exposed material is subjected to a second development with a blackand-white developer or colour developer. The processing is completed by fixing or bleach fixing the photographic material.
- Suitable compounds include those of the following formula:
- Suitable compounds are, for example, alkali metal or alkaline-earth metal boranocarbonates, especially sodium or potassium boranocarbonate.
- the compounds to be used according to the invention can be prepared by the process described in the Journal Inorganic Chemistry, vol. 6 (1967), pp. 817-822.
- the process according to the invention may be used in the production both of photographic black-and-white reversal images and photographic colour reversal images. Owing to the great practical importance of the last mentioned reversal process, the process according to the invention is preferably used in the production of colour reversal images.
- the photographic materials to be worked up may have the usual compositions.
- the materials used in the production of colour reversal images are multi-layer films on transparent support layers made, for example, of cellulose esters, polyesters or polycarbonates or multi-layer materials on paper supports.
- the usual colour reversal materials contain a blue sensitive silver halide emulsion layer with a colour coupler for the production of the yellow partial image, a green sensitive silver halide emulsion layer with a coupler for the production of the magenta partial image and a red sensitive silver halide emulsion layer with a colour coupler for the production of the cyan partial image.
- the process according to the invention is, of course, independent of the format of the colour photographic emulsion which is to be worked up. It can be used equally successfully for miniature films, narrow gauge colour photographic films or colour photographic paper.
- the process according to the invention can be used successfully in the production of coloured photographic images by the so-called silver dye bleaching process in r which layers which already contain the dye for the particular partial image are used in known manner.
- the dyes generally azo dyes, are then bleached in the dye bleaching bath in the areas corresponding to the silver image produced during development.
- the boranocarbonates to be used according to the invention can be introduced into the process in a bath containing an aqueous solution thereof preceding the second development; they may also be added to the second developer.
- these compounds can be used especially advantageously in the second developer without any harmful effects.
- the concentration of the boranocarbonates in the treatment baths may vary within wide limits. The optimum concentration can easily be found by a few simple tests and can be adapted according to the special requirements of the photographic material or of the reversal process. Quantities of between 0.05 and 5 g./l. of treatment bath have generally proved to be suiiicient. Concentrations of between 0.1 and 3 g. especially between 0.8 and 2.5 g. are preferred.
- the advantages of the process according to the invention lie in the excellent stability of the treatment baths which contain the chemical fogging agents.
- the intensity of the boranocarbonates as fogging agents is also of special importance since it lies in a particularly advantageous region so that complete development of the reverse materials obtained in accordance with the invention is possible without the photographic properties of the colour reversal materials being impaired in any way by excessive activity. Any dyes present, for example, are not attacked by the boranocarbonates.
- One special advantage which has hitherto not been observed with the use of chemical fogging agents is the improvement of the graininess which can in many cases be observed to be produced when employing the method according to the invention.
- EXAMPLE 1 A colour photographic multi-layered material having a red sensitive, a green sensitive and a blue sensitive silver halide emulsion layer containing colour couplers for the particular patrial images in the light sensitive layers is exposed in a sensitometer behind a grey step wedge in the usual manner.
- the exposed colour film is then developed in a blackand-white first developer solution of the following composition for 18 minutes at a temperature of 20 C.
- the film is then imersed for 4 minutes at a temperature of 19 C. in a stop bath consisting of a 3 sodium acetate solution which has been adjusted to pH 5.2 by the addition of acetic acid.
- Potassium boranocarbonate g 1.0 Sodium hexametaphosphate g 2.0 Sodium sulphite g 5.0 N,N-diethylparaphenylenediamine sulphate g 5.0 Hydroxylamine sulphate g 1.2 Potassium carbonate g 75.0 50% ethylene diamine ml 16 Water up to 1 litre.
- the colour developer is produced by first dissolving all the ingredients other than the potassium boranocarbonate, in 800 ml. of water. An aqueous solution of the fogging agent is then added and the solution is made up to 1000 ml. with water.
- the film is again washed for about 20 minutes and is then treated with the following bleaching bath.
- the pH of the bleaching bath is adjusted to 5.2 with acetic acid.
- the film is then again washed for about minutes and fixed for the same length of time in the following fixing bath.
- the processed material is immersed in a 0.2% aqueous solution of 2 ml. of tetrapropylene benzene sulphonate (pH not below 6.5) and then dried.
- the sensitometric comparison of the resulting positive step wedges shows that the procedure according to the invention is completely equivalent as regard gradation and sensitivity to the convensional method which includes a reversal re-exposure.
- the step wedge obtained by the procedure according to the invention has a considerably finer colour grain.
- EXAMPLE 2 A colour photographic reversal material on a layer support of paper is exposed in a sensitometer behind a step wedge.
- the material After immersion in a stop bath followed by washing, the material is treated with the following colour developer solution for 8 minutes at 20 C. without exposure.
- a light sensitive photographic multi-layer material which is suitable for use in the negative-positive process in the silver dye bleaching process, which contains diffusion-resistant azo dyes in the individual layers and which consists of a red sensitive silver bromide emulsion layer which is situated on the support layer and contains a cyan azo dye, a green sensitive silver bromide layer which contains a magenta dye, a yellow filter layer and an uppermost, blue sensitive silver bromide layer which contains a yellow dye, is exposed under an original to be copied and is then processed at 20 C. as follows:
- Potassium boranocarbonate has no effect on the dyes used. Image-wise reduction of the azo dyes in the second developer as is found, for example, with the known fogging agent, tin chloride, was not observed when using potassium boranocarbonate.
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 |
|---|---|---|---|
| DEA0058182 | 1968-02-14 | ||
| DE19681622258 DE1622258A1 (de) | 1968-02-14 | 1968-02-14 | Photographisches Umkehrverfahren |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3563746A true US3563746A (en) | 1971-02-16 |
Family
ID=25753810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US794397*A Expired - Lifetime US3563746A (en) | 1968-02-14 | 1969-01-27 | Use of boranocarbonates in a photographic reversal process |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3563746A (en)) |
| BE (1) | BE728385A (en)) |
| DE (1) | DE1622258A1 (en)) |
| FR (1) | FR2001902A1 (en)) |
| GB (1) | GB1195526A (en)) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5952159A (en) * | 1991-05-04 | 1999-09-14 | Agfa-Gevaert Ag | Method of photographic processing |
-
1968
- 1968-02-14 DE DE19681622258 patent/DE1622258A1/de active Pending
-
1969
- 1969-01-24 GB GB4065/69A patent/GB1195526A/en not_active Expired
- 1969-01-27 US US794397*A patent/US3563746A/en not_active Expired - Lifetime
- 1969-02-14 BE BE728385D patent/BE728385A/xx unknown
- 1969-02-14 FR FR6903640A patent/FR2001902A1/fr not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5952159A (en) * | 1991-05-04 | 1999-09-14 | Agfa-Gevaert Ag | Method of photographic processing |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1195526A (en) | 1970-06-17 |
| DE1622258A1 (de) | 1970-10-29 |
| FR2001902A1 (en)) | 1969-10-03 |
| BE728385A (en)) | 1969-08-14 |
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