US2401713A - Color photography - Google Patents
Color photography Download PDFInfo
- Publication number
- US2401713A US2401713A US528456A US52845644A US2401713A US 2401713 A US2401713 A US 2401713A US 528456 A US528456 A US 528456A US 52845644 A US52845644 A US 52845644A US 2401713 A US2401713 A US 2401713A
- Authority
- US
- United States
- Prior art keywords
- color
- ascorbic acid
- fog
- coupler
- emulsion
- 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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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
- G03C7/392—Additives
- G03C7/39208—Organic compounds
-
- 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
- the color formers may be added directly'to the emulsion layers as described by Fischer or they may be incorporated in a separate medium which is insoluble in the carrier'for the sensitive silver halide as described in Mannes and Godowsky U. S. Patent 2,304,940 granted December 15, 1942, and Jelley and Vittum U. S. Patent 2,322,027, granted June 15, 1943.
- a difficulty frequently encountered in these processes is the formation of color fog or stain.
- dye fog is formed along with the customary silver fog met in black-and-white photography but in addition fog is also formed from any oxidized developer formed by the action of air, oxidizing silver removal baths, etc. It is well known that in these processes the dye is formed when the silver halide is reduced to metallic silver, thereby oxidizing the developing agent to a form which couples with the color former. Once the developing agent is oxidized, it couples immediately with the color former whether a. photographic image is present or not.
- Aerial oxidation of the developer or oxidation by means other than the photographic image therefore, converts the developer to a form which will immediately react with the color former to produce a color fog or stain.
- Fog or stain arising from these causes is not readily controlled by the same procedures used to reduce or control silver ice.
- an object of the present invention to provide a means for stabilizing color forming developers toward aerial oxidation.
- a further object is to provide a means for reducing or eliminating the formation oi. color fog in photographic emulsions, particularly incorporated-coupler ing in a silver halide emulsion or in a color-forming developer solution, ascorbic acid in any of its tautomeric forms.
- the ascorbicacid may be incorporated in a developing solution containing a coupler or in a color developing solution containing no coupler and intended to be used for the development of incorporated-coupler materials, these sensitive materials containing the coupler in the emulsion layer.
- .By color developer we mean a developing solution containing as the developing agent a primary aromatic amino developing agent such asdiethyl-paraphenylene-diamine.
- color fog or stain in incorporated-coupler materials may be appreciably reduced by adding to the emulsion layers before coating or after coating and before processing an ascorbic acid, which has reducing properties and thereby tends to prevent the formation of color fog. It is believed that the ascorbic acid exerts an anti-oxidant action either by preventing the formation of extraneous oxidized developer or by reducing any extraneous oxidized developer before it has an opportunity to react with the color former. Whatever the mechanism of the reaction, .wehave found it possible in many cases to reduce markedly the fog or strain density without seriously affectingthe densities of the developed dye images. i
- the ascorbic acid When used in the emulsion layers, the ascorbic acid may be incorporated in a single layer coating or in one or more layers of a multi-layer coating. It may be desirable, for example, to have the ascorbic acid present in only one or two layers of a multi-layer coating.
- the ascorbic acid When used with emulsions containing a coupler dissolved in agents insoluble in gelatin as in the processes described in Mannes and Godowsky U. S. Patent 2,304,940 and Jelley and Vittum U. S. Patent 2,322,027, it may be added either to the emulsion itself or to the coupler-carrier along with the coupler.
- the ascorbic acids may be used in the emulsion in quantities ranging from 0.1 gram to 1 gram per liter of gelatino-silver halide emulsion.
- the quantities used may vary from 0.05 gram to 0.5 gram per liter of solution.
- the reducing agent may be added to one of the film processing baths such as a prebath or the first developer bath.
- the first deyeloper is a color-forming developer.
- the reducing agent may, therefore, be used in a color-forming developer such as a diethyl-p-phenylenediamine developer.
- Our method is intended for use principally with emulsions which produce a negative image upon direct development, that is, emulsions in which a negative image would be formed upon development after exposure under a positive image or in which positive images would be formed on direct development after exposure under a negative image. It may also be used for reversal color development.
Description
Patented June 4, 1946 COLOR PHOTOGRAPHY Paul WrVittum and Lot S. Wilder, Rochester, N. Y., assignors to Eastman Kodak Company. Rochester, N. Y., acorporation of New Jersey Serial No. 528,456
No Drawing. Application March 28, 1944,
3 Claims. 1
as phenolic hydroxyl compounds or compounds,
with reactive methylene groups, which are capable of reacting with the development product of aromatic amino photographic developers to produce dyes, The color formers may be added directly'to the emulsion layers as described by Fischer or they may be incorporated in a separate medium which is insoluble in the carrier'for the sensitive silver halide as described in Mannes and Godowsky U. S. Patent 2,304,940 granted December 15, 1942, and Jelley and Vittum U. S. Patent 2,322,027, granted June 15, 1943.
A difficulty frequently encountered in these processes is the formation of color fog or stain. With materials in which color forming compounds are incorporated in the sensitive layer, dye fog is formed along with the customary silver fog met in black-and-white photography but in addition fog is also formed from any oxidized developer formed by the action of air, oxidizing silver removal baths, etc. It is well known that in these processes the dye is formed when the silver halide is reduced to metallic silver, thereby oxidizing the developing agent to a form which couples with the color former. Once the developing agent is oxidized, it couples immediately with the color former whether a. photographic image is present or not. Aerial oxidation of the developer or oxidation by means other than the photographic image, therefore, converts the developer to a form which will immediately react with the color former to produce a color fog or stain. Fog or stain arising from these causes is not readily controlled by the same procedures used to reduce or control silver ice.
It is, therefore, an object of the present invention to provide a means for stabilizing color forming developers toward aerial oxidation. A further object is to provide a means for reducing or eliminating the formation oi. color fog in photographic emulsions, particularly incorporated-coupler ing in a silver halide emulsion or in a color-forming developer solution, ascorbic acid in any of its tautomeric forms. 1 The ascorbicacid may be incorporated in a developing solution containing a coupler or in a color developing solution containing no coupler and intended to be used for the development of incorporated-coupler materials, these sensitive materials containing the coupler in the emulsion layer. .By color developer we mean a developing solution containing as the developing agent a primary aromatic amino developing agent such asdiethyl-paraphenylene-diamine.
We have found that color fog or stain in incorporated-coupler materials may be appreciably reduced by adding to the emulsion layers before coating or after coating and before processing an ascorbic acid, which has reducing properties and thereby tends to prevent the formation of color fog. It is believed that the ascorbic acid exerts an anti-oxidant action either by preventing the formation of extraneous oxidized developer or by reducing any extraneous oxidized developer before it has an opportunity to react with the color former. Whatever the mechanism of the reaction, .wehave found it possible in many cases to reduce markedly the fog or strain density without seriously affectingthe densities of the developed dye images. i
Compounds which we have found suitable for use according to our invention include 1-ascorbic acid and d-isoascorbic acid. These compounds have the following formula:
CH- H-CHzOH HOO/ When used in the emulsion layers, the ascorbic acid may be incorporated in a single layer coating or in one or more layers of a multi-layer coating. It may be desirable, for example, to have the ascorbic acid present in only one or two layers of a multi-layer coating. When the ascorbic acid is used with emulsions containing a coupler dissolved in agents insoluble in gelatin as in the processes described in Mannes and Godowsky U. S. Patent 2,304,940 and Jelley and Vittum U. S. Patent 2,322,027, it may be added either to the emulsion itself or to the coupler-carrier along with the coupler.
In general, the ascorbic acids may be used in the emulsion in quantities ranging from 0.1 gram to 1 gram per liter of gelatino-silver halide emulsion. When used in the developing solution or other bath, the quantities used may vary from 0.05 gram to 0.5 gram per liter of solution. These values are illustrative only.
The following examples illustrate color-forming developers containing ascorbic acid:
1. Diethyl p-phenylene dianiine grams 4.0 Potassium bromide ..do 1.0 Sodium sulfite "do--." 0.5 d-Iso-ascorbic acid -do 0.2
Sodium carbonate do 80.0 Water to liters 1.0
2. Diethyl p-phenylene diamine- "grams" 6.0 Potassium bromide do 2.0 d-Iso-ascorbic acid do 0.3 Sodium carbonate -do 80.0 Sodium hydroxide do- 4.0 Water to liters 1.0
3. Sodium hexametaphosphate ....grarns 1.0
.Soclium sulfite-. do 4.0
2-amino-5-diethylaminotoluene HCl l l grams 3.0 Sodium carbonate (anhydrous) do 10.0 Sodium metaborate do 40.0 Potassium bromide do 0.8 5-methyl benzotriazoleni; d0 0.03 d-Iso-ascorbic acid do 0.2
Water to H--. ....liters-'.. 1.0
4. Water -1. cc 800.0 Sodium'sulfite (anhydrous) grams 25.0 2-amino-5-diethylaminotoluene HCl grams" 1.2
Sodium carbonate do 20.0
Potassium bromide do 1.5
Sodium thiocyanate do 4.0
, Sodium hydroxide ..do 4.0
S-nitro-benzimidazole nitrate -do 0.30 2,6-dibromo 1,5 dihydroxy naphthalene grams.. 1.5
d-Iso-ascorbic acid -do.... 0.2
Water to liters 1.0
The reducing agent may be added to one of the film processing baths such as a prebath or the first developer bath. In the case oi negative development as disclosed. for example, in Jelley and Vittum U. S. Patent 2,322,027, the first deyeloper is a color-forming developer. The reducing agent may, therefore, be used in a color-forming developer such as a diethyl-p-phenylenediamine developer.
Our method is intended for use principally with emulsions which produce a negative image upon direct development, that is, emulsions in which a negative image would be formed upon development after exposure under a positive image or in which positive images would be formed on direct development after exposure under a negative image. It may also be used for reversal color development.
Our process is particularly useful with paper materials, where it is especially important to reduce the minimum (fog) densities. This applies ,both to negative-developed paper and to reversal paper and transparency materials.
It will be understood that the examplesand modifications disclosed herein are by way of example only and that our invention is to be taken as limited only by the scope of the appended claims.
We claim:
i 1. The method of preventing the formation of color fog in a photographic silver halide emulsion which contains a non-difiusing coupler therein, comprising developing said emulsion after exposure with a primary aromatic amino developing agent in the presence of an ascorbic acid. 2. The method of preventing the formation of color fog in a photographic silver halide emulsion which produces a negative image on development andwhich contains anon-diffusing coupler there in, comprising developing said emulsion after exposure with a primary aromatic amino developing agent in the presence of ascorbic acid.
3. The method of preventing the formation of color fog in a photographic silver halide emulsion which produces a negative image on development and which contains a non-diffusing coupler therein, comprising exposing said emulsion and developing it in a solution containing a primary aromatic amino developing agent and ascorbic acid.
PAUL W. VITTUM. LOTS. WILDER.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US404894A US2360290A (en) | 1941-07-31 | 1941-07-31 | Preventing formation of color fog in emulsions |
US528456A US2401713A (en) | 1941-07-31 | 1944-03-28 | Color photography |
FR952440D FR952440A (en) | 1941-07-31 | 1947-07-22 | Improvements to processes to avoid haze during the development of photographic emulsions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US404894A US2360290A (en) | 1941-07-31 | 1941-07-31 | Preventing formation of color fog in emulsions |
US528456A US2401713A (en) | 1941-07-31 | 1944-03-28 | Color photography |
Publications (1)
Publication Number | Publication Date |
---|---|
US2401713A true US2401713A (en) | 1946-06-04 |
Family
ID=27018821
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US404894A Expired - Lifetime US2360290A (en) | 1941-07-31 | 1941-07-31 | Preventing formation of color fog in emulsions |
US528456A Expired - Lifetime US2401713A (en) | 1941-07-31 | 1944-03-28 | Color photography |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US404894A Expired - Lifetime US2360290A (en) | 1941-07-31 | 1941-07-31 | Preventing formation of color fog in emulsions |
Country Status (2)
Country | Link |
---|---|
US (2) | US2360290A (en) |
FR (1) | FR952440A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2656272A (en) * | 1950-11-30 | 1953-10-20 | Gen Aniline & Film Corp | Stabilized azine photographic developers containing sodium metaborate as the sole alkali |
US2923627A (en) * | 1957-04-17 | 1960-02-02 | Ilford Ltd | Colour photography |
US3383215A (en) * | 1963-07-19 | 1968-05-14 | Ilford Ltd | Antifogging combination of iso-ascorbic acid and 2 to 15 g. of hydroquinone |
US5098805A (en) * | 1987-01-28 | 1992-03-24 | Fuji Photo Film Co., Ltd. | Color photographs, a process for preparing them and color photographic material employed therefor |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2440954A (en) * | 1945-08-23 | 1948-05-04 | Du Pont | Process for eliminating stain from color-yielding elements by treatment with aromatic aldehydes containing an acyl group |
US2571725A (en) * | 1946-08-15 | 1951-10-16 | Eastman Kodak Co | Eliminating stain in photographic color material |
US2577127A (en) * | 1946-11-23 | 1951-12-04 | Du Pont | Photographic element with colloid layer containing color former and nonionic wettingagent |
BE530383A (en) * | 1951-04-10 | |||
BE516242A (en) * | 1951-12-15 | |||
BE519219A (en) * | 1952-04-15 | |||
BE529275A (en) * | 1953-06-03 | |||
US2735765A (en) * | 1953-06-03 | 1956-02-21 | Ch-chs | |
BE529273A (en) * | 1953-06-03 | |||
BE532579A (en) * | 1953-10-16 | |||
US3287133A (en) * | 1963-03-01 | 1966-11-22 | Eastman Kodak Co | Photographic dye developer dispersions utilizing water-soluble sulfites |
US3432300A (en) * | 1965-05-03 | 1969-03-11 | Eastman Kodak Co | 6-hydroxy chromans used as stabilizing agents in a color photographic element |
US3902905A (en) * | 1972-11-20 | 1975-09-02 | Eastman Kodak Co | Photographic elements containing image dye-providing layer units |
JPS5334043B2 (en) * | 1974-02-06 | 1978-09-19 | ||
DE2732971A1 (en) * | 1977-07-21 | 1979-02-01 | Agfa Gevaert Ag | ANTI-COLOR VEIL FOR COLOR PHOTOGRAPHIC MATERIALS |
JPS599657A (en) * | 1982-07-07 | 1984-01-19 | Fuji Photo Film Co Ltd | Silver halide color photosensitive material |
JPS59116647A (en) | 1982-12-13 | 1984-07-05 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
JPS60143331A (en) | 1983-12-29 | 1985-07-29 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
EP0209118B1 (en) | 1985-07-17 | 1991-10-23 | Konica Corporation | Silver halide photographic material |
JPS6267536A (en) * | 1985-09-19 | 1987-03-27 | Konishiroku Photo Ind Co Ltd | Method of giving light fastness to organic coloring matter |
JP2516026B2 (en) | 1986-08-15 | 1996-07-10 | 富士写真フイルム株式会社 | Silver halide photosensitive material |
US5434041A (en) * | 1993-04-02 | 1995-07-18 | Eastman Kodak Company | Photographic elements containing particular color couplers in combination with hydroquinone type stabilizers |
DE69129964T2 (en) * | 1990-10-08 | 1999-01-21 | Fuji Photo Film Co Ltd | A silver halide color photographic material |
US5198517A (en) * | 1991-08-06 | 1993-03-30 | Eastman Kodak Company | Polymeric scavengers for oxidized developing agents and photographic elements containing the same |
US5376520A (en) | 1992-12-07 | 1994-12-27 | Konica Corporation | Silver halide light sensitive color photographic material |
US5545514A (en) * | 1994-07-14 | 1996-08-13 | Konica Corporation | Silver halide light-sensitive color photographic material |
JP3584119B2 (en) | 1996-04-05 | 2004-11-04 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
-
1941
- 1941-07-31 US US404894A patent/US2360290A/en not_active Expired - Lifetime
-
1944
- 1944-03-28 US US528456A patent/US2401713A/en not_active Expired - Lifetime
-
1947
- 1947-07-22 FR FR952440D patent/FR952440A/en not_active Expired
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2656272A (en) * | 1950-11-30 | 1953-10-20 | Gen Aniline & Film Corp | Stabilized azine photographic developers containing sodium metaborate as the sole alkali |
US2923627A (en) * | 1957-04-17 | 1960-02-02 | Ilford Ltd | Colour photography |
US3383215A (en) * | 1963-07-19 | 1968-05-14 | Ilford Ltd | Antifogging combination of iso-ascorbic acid and 2 to 15 g. of hydroquinone |
US5098805A (en) * | 1987-01-28 | 1992-03-24 | Fuji Photo Film Co., Ltd. | Color photographs, a process for preparing them and color photographic material employed therefor |
Also Published As
Publication number | Publication date |
---|---|
US2360290A (en) | 1944-10-10 |
FR952440A (en) | 1949-11-16 |
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