US3645737A - Silver halide photographic processing using formazans - Google Patents
Silver halide photographic processing using formazans Download PDFInfo
- Publication number
- US3645737A US3645737A US793553*A US3645737DA US3645737A US 3645737 A US3645737 A US 3645737A US 3645737D A US3645737D A US 3645737DA US 3645737 A US3645737 A US 3645737A
- Authority
- US
- United States
- Prior art keywords
- color
- silver halide
- photographic material
- silver
- cooh
- 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
- -1 Silver halide Chemical class 0.000 title claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 title abstract description 29
- 239000004332 silver Substances 0.000 title abstract description 29
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 abstract description 32
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 8
- 239000000839 emulsion Substances 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 abstract description 3
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 20
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000975 dye Substances 0.000 description 11
- CSGQJHQYWJLPKY-UHFFFAOYSA-N CITRAZINIC ACID Chemical compound OC(=O)C=1C=C(O)NC(=O)C=1 CSGQJHQYWJLPKY-UHFFFAOYSA-N 0.000 description 9
- 230000003381 solubilizing effect Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 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 2
- KURBTRNHGDQKOS-XNWCZRBMSA-N n-[(e)-ethylideneamino]aniline Chemical compound C\C=N\NC1=CC=CC=C1 KURBTRNHGDQKOS-XNWCZRBMSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- ZCGVPUAAMCMLTM-UHFFFAOYSA-N 2-amino-5-chlorobenzenesulfonic acid Chemical compound NC1=CC=C(Cl)C=C1S(O)(=O)=O ZCGVPUAAMCMLTM-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/407—Development processes or agents therefor
- G03C7/413—Developers
Definitions
- ABSTRACT This application describes a process of color development of color photographic material wherein at least one silver halide emulsion layer containing a developable silver salt is color developed to yield a dye image, the developed silver and the residual silver halide being removed, the step of developing the photographic material with a color developing solution in the presence of an image-forming color coupler and a forcompound of the formula:
- R and R are each selected from hydrogen atoms or solubilising groups and R is a hydrogen atom or an aryl, alkyl, aralkyl or :1 CN group or a solubilising group selected from COOH, CH SO H or CH COOH, at least one of R R or R being a solubilising group, the two lbw 519925 QBEPFQRUPEXUPE er ile u t lqem I 7 Claims, No Drawings SILVER HALIDE PHOTOGRAPHIC PROCESSING USING F ORMAZANS This invention relates to color development processes for the production of color images in photographic material.
- the oxidized color developing agent When photographic material containing in each emulsion layer a relatively large amount of silver halide and a substantive coupler is exposed and developed in the presence of such a competing coupler which may be added to the emulsion layer but more usually to the developer, the oxidized color developing agent combines with both couplers.
- the competing coupler yields a dye which is nonsubstantive and water soluble and is removed from the film in the developer solution and subsequent washing steps.
- the substantive coupler yields a substantive dye image of the density required but being derived from a greater number of silver halide grains shows an improved graininess compared to images obtained from material wherein less silver halide is present initially.
- R, and R are each selected from hydrogen atoms or solubilizing groups and R is a hydrogen atom or an aryl, alkyl, aralkyl or a -CN group or a solubilizing group selected from COOH, -CH SO;,H or CH COOH, at least one of R ,'R or R being a solubilizing group, the two phenyl groups optionally carrying further substituents.
- solubilizing groups are SO H, CH SO H. -COOH, CH COOH, -O-CH COOH.
- the formazan compound of the above defined formula whether present initially in the photographic material or present in the color developing solution is able to couple with oxidized color developing agent to form a colorless product.
- the colorless product is the derived tetrazolium salt.
- the formazans used in the process of the present invention are colored yellow to red in alkaline solution but due to their great solubility and lack of affinity for gelatin very little if any remains in the photographic material after the washing step which follows color development. However if any does remain in the photographic material it is oxidized to a colorless compound in the bleaching bath, as a bleaching step is present as hereinafter described in all types of color processing, in order to remove the developed silver from the material.
- the process of the present invention is particularly of use in the processing of a multilayer color material of the type in which there are three gelatino silver halide emulsion layers, selectively sensitive to blue, green and red regions of the spectrum, each layer containing a color coupler substantive thereto, which yields on color development a dye image complementary in color to the color sensitivity of the layer containing it.
- the color material may be of the type which yields a direct color image on development or may be of the type which is used to produce reversal color images. It is also applicable in the reversal processing of color photographic material wherein the image-forming color couplers are not present initially but are present in each color developing solutron.
- the compounds of the above formula are present in the color developing solution or solutions but they may be present initially in the photographic material and in this case preferably in each silver halide containing layer.
- the compounds of the above formula are present in the color developing solution they are preferably present at a concentration of 0.5 to 5 g./liter. In the case of substantivecolor-coupler material the exact concentration depends on the desired effect and on the silver halide/color coupler coating weight.
- Example 1 which relates to a reversal material containing substantive color couplers a color development bath of the following composition was used:
- the diazotized suspension is added to a stirred solution of 140' parts of acetaldehyde phenyl hydrazone in 2,000 parts of pyridine keeping the temperature below 5 C. After stirring for 30 minutes the deep red solution is acidified to Congo Red paper with concentrated hydrochloric acid keeping the temperature below 'l0 C. A further 472 parts of concentrated hydrochloric acid are added to precipitate the product fully.: After collection by filtration the formazan dye is washed with 2N hydrochloric acid and then acetone. After drying at 50 C. 268 parts of a bluish grey powder are obtained which dissolves readily in dilute sodium carbonate to give a yellow solution.
- Strips were washed, acid stopped, bleached, washed, fixed, washed and conditioned in the normal manner. Strips ;were also processed with the addition of 2 g. of Compound I l-3'-sulphophenyl-3-methyl-5-formazan) to 1 liter of the color developing solution. Strips were also processed with the addition of 2 g. of citrazinic acid to 1 liter of the color Zdeveloping solution. A further set of strips was processed in the same color developing solutions which had been allowed ;to stand for 4 days. The following results were obtained on measurement of the maximum density of the strips to a green filter.
- the formazan like citrazinic acid, is effective in reducing the density and contras of the color developed layers.
- This higher silver coating weight material processed with either the formazan or citrazinic acid] gives a better grainiriess in general than a conventionall i coated and processed material.
- upward adjustment of silver coating weights to give a material balanced for processing with the formazan will give. a better graininess than a material balanced for processing with citrazinic acid.
- Compounds ll to V have the general formula in the preparation of Compound I acetaldehydephenylhydrazone is replaced by an equivalent amount of acetaldehydephenylhydrazone-4-carboxylic acid to give compound, VI. in similar fashion, by the reaction of diazotised orthanilici acid, sulphanilic acid, 4-aminobenzoic acid and 4- chloroaniline-2-sulphonic acid with acetaldehydephenylhydrazone-4-carboxylic acid there are obtained the formazan compounds Vll, Vlll, lX and X respectively.
- R and R are each hydrogen or a solubilizing group selected from --SO H, CH SO H, COOH, CH COOl-l or --OCH COOH and R is a hydrogen atom or an aryl, alkyl, aralkyl or a CN group or a solubilizing group selected from COOH, CH SO H or CH COOH, at least one of R,, R or R being a solubilizinggroup as defined, or a corresponding iormazan compoun in which at least one of the where R, and R are each hydrogen or a solubilizing group selected from SO H, CH SO H, COOH, CH COOH or -O--CH COOl-l and R is a hydrogen atom or an aryl, alkyl, aralkyl or a CN group or a solubilizing group selected from COOH, -CH SO H or CH COOH, at least one of R,, R or R being a solubilizing group as defined, or a corresponding formazan compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4303/68A GB1205081A (en) | 1968-01-26 | 1968-01-26 | Colour photography |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3645737A true US3645737A (en) | 1972-02-29 |
Family
ID=9774620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US793553*A Expired - Lifetime US3645737A (en) | 1968-01-26 | 1969-01-23 | Silver halide photographic processing using formazans |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3645737A (xx) |
| BE (1) | BE727411A (xx) |
| GB (1) | GB1205081A (xx) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3168400A (en) * | 1961-05-22 | 1965-02-02 | Eastman Kodak Co | Rapid processing of photographic color materials |
| US3467520A (en) * | 1964-03-20 | 1969-09-16 | Agfa Ag | Production of colored direct positive photographic images |
| US3503741A (en) * | 1966-11-04 | 1970-03-31 | Eastman Kodak Co | Silver-dye-bleach process utilizing formazan dyes |
-
1968
- 1968-01-26 GB GB4303/68A patent/GB1205081A/en not_active Expired
-
1969
- 1969-01-23 US US793553*A patent/US3645737A/en not_active Expired - Lifetime
- 1969-01-24 BE BE727411D patent/BE727411A/xx unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3168400A (en) * | 1961-05-22 | 1965-02-02 | Eastman Kodak Co | Rapid processing of photographic color materials |
| US3467520A (en) * | 1964-03-20 | 1969-09-16 | Agfa Ag | Production of colored direct positive photographic images |
| US3503741A (en) * | 1966-11-04 | 1970-03-31 | Eastman Kodak Co | Silver-dye-bleach process utilizing formazan dyes |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1205081A (en) | 1970-09-16 |
| BE727411A (xx) | 1969-07-01 |
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