US2396396A - Production of colored photographic images - Google Patents
Production of colored photographic images Download PDFInfo
- Publication number
- US2396396A US2396396A US510373A US51037343A US2396396A US 2396396 A US2396396 A US 2396396A US 510373 A US510373 A US 510373A US 51037343 A US51037343 A US 51037343A US 2396396 A US2396396 A US 2396396A
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- photographic
- color
- image
- developing
- production
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- 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
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
- G03C7/38—Couplers containing compounds with active methylene groups in rings
- G03C7/381—Heterocyclic compounds
- G03C7/3815—Heterocyclic compounds with one heterocyclic ring
Definitions
- This invention relates to the production of colored photographic images.
- an image of metallic silver there is formed an image of metallic silver.
- a suitable substance known as, a color-former, which will react with the oxidation product of the developer to produce a dyestufl' there is also formed simultaneously a colored photographic image.
- the colored image may be revealed by removal of the silver image by treatment with a suitable bleaching agent, for example with that known as Farmer's reducer.
- I produce a photographic dyestuif image in a photographic element either by developing a reducible silver salt contained in the element with an aromatic amino developing agent, as defined hereinafter, in the presence of a color former which is a 2:4- diarylpyrrole of the formula where R and R.
- aryl radicals for example of the benzene or naphthalene series, substituted or not, the same or difierent, and where R stands for hydrogen or for a non-reactive substituent, for example an aryl-, alkyl-, allgylamino-, benzylideneaminoor acylaminqradical, or by treatin a photographic element containing such color former with an oxidation product of such a developing agent or with a p-nitrosodialkylaniline or with a diazonium salt.
- aromatic amino developing agents used are those which are capable of developing silver halide photographic emulsions and which are or p-phenylene diamines-or derivatives thereof containing at least one unsubstituted aminogroup, or 0- or p-amino phenols or derivatives thereof containing an unsubstituted amino group.
- Examples of such developing agents which may be used include p-aminodii'nethylaniline, p-aminodiethylaniline, p-amino di-n-butylaniline, p methylaminoaniline, p ethylaminoaniline, chloro-p-phenylenediamine, 1 2 5-toluylenediamine, 2-amino-5-diethylaminotoluene, N-paminophenylpiperidine, N-methyl-N-p-hydroxyethyl-p-phenylenediamine, N-n-butyl-N- p-hydroxyethyl-p-phenylenediamine, py-dihydroxy- February 10, 1943.
- the 2:4-diarylpyrro1es which may be used as color formers according to the invention include. for example, 2:4-diphenylpyrrole, 2-(p-methoxyphenyl) -4-phenylpyrrole, 2- (m-hydroxyphenyl) 4-phenylpyrrole, 2-(o-chloropheny1) -4-phenylpyrrole, 2- (p-acetylaminophenyl) -4-phenylpyrrole, 2-e-naphthyl-4-phenylpyrrole, 2-phenyl-4- B naphthylpyrrole, 2:3:4 triphenylpyrrole, 3-
- the 2:4-diarylpyrro1es which are used as color formers may be made, for example, by the processes described in the specifications of applications Nos. 16,277/41 and 3,583/42, new British Patent No. 556,156 and in the corresponding United States applications Serial No. 457,229, filed September 3, 1942, and Serial No. 475,434, filed Those 2:4-diarylpyrroles which bear in the 3-position an amino or substituted amino group may be made as is described, for example, in the case of 3-benzoylamino-2z4- diphenylpyrrole, by Gabriel, in Berichte der wholesome chemischen Deutschenmaschine, 41, 1138.
- the sulphonic acid derivatives of the 2:4-diarylpyrroles may be made, for example, as is described in the specification of application No. 9,689/42 and corresponding United States applition Serial No. 482,479, filed April 9, 1943,
- the photographic dyestufi image may be produced by developing a reducible silver salt image with an aromatic amino developing agent in the presence of the color formers of the invention.
- the color formers may be present in the developing solution or they may be incorporated in the photographic elements.
- Those sulphonic acid derivatives of the aforesaid 2:4-diarylpyrroles and their salts which are water-soluble are especially suitable for use in the developing solution.
- Those color formers which are not sulphonic acid derivatives are frequently but sparingly soluble in water. Nevertheless, especially when they contain other solubilising groups, for example phenol groups, they may frequently be incorporated in developing solutions by the use of suitable proportions of an organic solvent which is miscible purpose. Being also sparingly soluble in water they have little tendency to diffuse from the film into the processing solutions.
- the color formers of the invention may be incorporated in the photographic emulsions by any of the well known methods, for example by the processes described in British specifications Nos. 540,368 and 541,558.
- the images obtained using the color formers of the invention are of bright reddish blue to blue-green shades. These shades are of high intensity and, furthermore, they are of high intensity when, as is desirably the case, photographic developing solutions are used which contain an alkali metal sulphite.
- the photographic images are produced in photograpic elements containing a reducible silver salt image by development with an aromatic amino developing agent.
- an element containing the color former may be treated with the oxidation product of an aromatic amino developing agent.
- the color former may be incorporated in bichromate-sensitised colloid layers, for example gelatin. gum arabic or albumen, the layers exposed, the unexposed colloid removed, for example by treatment with hot water, and the color developed in the exposed portions by treatment with a p-nitrosodialkylaniline or a derivative thereof.
- photographic elements containing the color formers of the invention may be treated with diazonium salts to form azo dyes.
- the-color formers of this invention yield yellow or red dyes which may readily be differentially bleached to form dye images, for example by the processes of British specifications Nos. 133,034 and 496,558.
- Example 1 To 1000 cc. of a developer having the followthere is added 100 ccs. of a solution of 1.0 gram of 2-phenyl-4-(m-hydroxylphenyl)pyrrole and 2.9 grams of sodium hydroxide in 100 cos. of a mixture of equal weights of water and ethanol.
- Example 2 1.0 gram of the sodium salt of 2-phenyl-4- (o-chlorophenyl)pyrrole monosulphonic acid is dissolved in 100 ccs. of hot .water and the solution is added to 1000 cos. of the developing solution vused in Example 1.
- Example 3 1.0 gram of the ammonium salt of 2:4-diphenylpyrrole monosulphonic acid is dissolved in a mixture of 50 ccs. of water and 50 ccs. of acetone. A further 50 cos. of acetone are added to the solutionand the resulting mixture is added to 1000 ccs. of a developer of the following composition:
- a photographic element containing a developable silver halidev image is treated with the above solution and a bright blue dye image is obtained together with the silver image.
- Example 5 To 1000 ccs. of the developing solution used in Example 1 thereis added 100 ccs. of acetone and the resulting mixture is employed as a developer for a photographic element containing a ducible silver salts is developed in this solution a bright greenish-blue dye image is produced together with metallic silver.
- the silver may be reducible silver salt and also containing 2-phenyl- 4-(2-chlorophenyl) pyrrole in the form of a fine uniform dispersion. A bright greenish-blue dye image is obtained along with the silver image.
- Photographic elements containing other color formers are developed in the developing solution used in Example 5.
- the color of the dye image obtained is shown in the table below:
- a process for the production of a photographic dyestufi image which comprises developing a photographic element containing a reducible silver salt image with an aromatic primary amino color developing agent in the presence of a substituted 2 l-diarylpyrrole of the formula where R and R stand for aryl radicals and R stands for a member of the group consisting of hydrogen, aryl, alkyl, alkylamino, benzylideneamino, and acylamino radicals.
- a photographic element bearing an emulsion layer containing a light-sensitive material and a color former comprising a 2:4-diarylpyrrole of the formula where R and R stand for aryl radicals and R stands for a member of the group consisting of hydrogen, aryl, alkyl, alkylamnio, benzylideneamino, and acylamino radicals.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Pyrrole Compounds (AREA)
Description
Patented Mar. 12, 1946 PRODUCTION OF COLORED PHOTOGRAPHIC IMAGES Douglas William Stammers,
Blackley, Mancheater, England, minor to Imperial ChemicBarll Industries Limited, a corporation of Great No Drawing. Application November 15, 1943, Se-
rial No. 510,373. 25, 1942 In Great Britain November 4 Claims. (Cl. 95-6) This invention relates to the production of colored photographic images.
It is known that when a photographic silver halide emulsion is developed by treatment with an aromatic amino developing agent, for example, an asymmetric dialkyl p-phenylenediamine,
there is formed an image of metallic silver. It is also known that when there is present also in the developing solution or in the silver halide emulsion a suitable substance, known as, a color-former, which will react with the oxidation product of the developer to produce a dyestufl' there is also formed simultaneously a colored photographic image. The colored image may be revealed by removal of the silver image by treatment with a suitable bleaching agent, for example with that known as Farmer's reducer.
According to the present invention I produce a photographic dyestuif image in a photographic element either by developing a reducible silver salt contained in the element with an aromatic amino developing agent, as defined hereinafter, in the presence of a color former which is a 2:4- diarylpyrrole of the formula where R and R. stand for aryl radicals for example of the benzene or naphthalene series, substituted or not, the same or difierent, and where R stands for hydrogen or for a non-reactive substituent, for example an aryl-, alkyl-, allgylamino-, benzylideneaminoor acylaminqradical, or by treatin a photographic element containing such color former with an oxidation product of such a developing agent or with a p-nitrosodialkylaniline or with a diazonium salt.
The aromatic amino developing agents used are those which are capable of developing silver halide photographic emulsions and which are or p-phenylene diamines-or derivatives thereof containing at least one unsubstituted aminogroup, or 0- or p-amino phenols or derivatives thereof containing an unsubstituted amino group.
Examples of such developing agents which may be used include p-aminodii'nethylaniline, p-aminodiethylaniline, p-amino di-n-butylaniline, p methylaminoaniline, p ethylaminoaniline, chloro-p-phenylenediamine, 1 2 5-toluylenediamine, 2-amino-5-diethylaminotoluene, N-paminophenylpiperidine, N-methyl-N-p-hydroxyethyl-p-phenylenediamine, N-n-butyl-N- p-hydroxyethyl-p-phenylenediamine, py-dihydroxy- February 10, 1943.
propyl-p-phenylenediamine and N:N-diethyl-ophenylenediamine.
The 2:4-diarylpyrro1es which may be used as color formers according to the invention include. for example, 2:4-diphenylpyrrole, 2-(p-methoxyphenyl) -4-phenylpyrrole, 2- (m-hydroxyphenyl) 4-phenylpyrrole, 2-(o-chloropheny1) -4-phenylpyrrole, 2- (p-acetylaminophenyl) -4-phenylpyrrole, 2-e-naphthyl-4-phenylpyrrole, 2-phenyl-4- B naphthylpyrrole, 2:3:4 triphenylpyrrole, 3-
benzoylamino-2-:4-diphenylpyrrole, 3-acetylamino-2 4-diphenylpyrrole and 3- benzoylamino-2 4- di-p-tolylpyrrole. The sulphonic acid derivatives of the 2:4-diaryl pyrroles, for example of those listed above, and their salts, may also be used.
The 2:4-diarylpyrro1es which are used as color formers may be made, for example, by the processes described in the specifications of applications Nos. 16,277/41 and 3,583/42, new British Patent No. 556,156 and in the corresponding United States applications Serial No. 457,229, filed September 3, 1942, and Serial No. 475,434, filed Those 2:4-diarylpyrroles which bear in the 3-position an amino or substituted amino group may be made as is described, for example, in the case of 3-benzoylamino-2z4- diphenylpyrrole, by Gabriel, in Berichte der deutschen chemischen Gesellschaft, 41, 1138. The sulphonic acid derivatives of the 2:4-diarylpyrroles may be made, for example, as is described in the specification of application No. 9,689/42 and corresponding United States applition Serial No. 482,479, filed April 9, 1943,
As said the photographic dyestufi image may be produced by developing a reducible silver salt image with an aromatic amino developing agent in the presence of the color formers of the invention.
' The color formers may be present in the developing solution or they may be incorporated in the photographic elements. Those sulphonic acid derivatives of the aforesaid 2:4-diarylpyrroles and their salts which are water-soluble are especially suitable for use in the developing solution. Those color formers which are not sulphonic acid derivatives are frequently but sparingly soluble in water. Nevertheless, especially when they contain other solubilising groups, for example phenol groups, they may frequently be incorporated in developing solutions by the use of suitable proportions of an organic solvent which is miscible purpose. Being also sparingly soluble in water they have little tendency to diffuse from the film into the processing solutions. The color formers of the invention may be incorporated in the photographic emulsions by any of the well known methods, for example by the processes described in British specifications Nos. 540,368 and 541,558.
The images obtained using the color formers of the invention are of bright reddish blue to blue-green shades. These shades are of high intensity and, furthermore, they are of high intensity when, as is desirably the case, photographic developing solutions are used which contain an alkali metal sulphite.
As is known, many of the blue-green images obtained from known color formers, which should, ideally. transmit all light of 400-500 ma. wave length do in fact absorb appreciably in this region. Thus for example in making copies from colored originals by methods in which no color correction by masking is introduced, there is thereby introduced a shift of hue whereby in effect there issuperimposed yellow over the blue areas of the copy. I have found that certain of the color formers of this invention, particularly those in which the aryl groups of the 2:4-diaryipyrroles are substituted by chlorine atoms, give rise to dye images which show an improved transmission in the 400-500 ma, 1. e., blue, region.
As illustrated in the examples which follow the photographic images are produced in photograpic elements containing a reducible silver salt image by development with an aromatic amino developing agent. But, as already stated, alternative methods may be used. Thus an element containing the color former may be treated with the oxidation product of an aromatic amino developing agent. For example the color former may be incorporated in bichromate-sensitised colloid layers, for example gelatin. gum arabic or albumen, the layers exposed, the unexposed colloid removed, for example by treatment with hot water, and the color developed in the exposed portions by treatment with a p-nitrosodialkylaniline or a derivative thereof.
Furthermore, photographic elements containing the color formers of the invention may be treated with diazonium salts to form azo dyes. Thus when treatedwith benzene diazonium chloride the-color formers of this invention yield yellow or red dyes which may readily be differentially bleached to form dye images, for example by the processes of British specifications Nos. 133,034 and 496,558.
The invention is illustrated but not limited by the following examples:
Example 1 To 1000 cc. of a developer having the followthere is added 100 ccs. of a solution of 1.0 gram of 2-phenyl-4-(m-hydroxylphenyl)pyrrole and 2.9 grams of sodium hydroxide in 100 cos. of a mixture of equal weights of water and ethanol.
When a photographic element containing reremoved from the element by successive bathing in a 4% aqueous solution of potassium ferricyanide and in a 25% aqueous solution of sodium thiosulphate.
Example 2 1.0 gram of the sodium salt of 2-phenyl-4- (o-chlorophenyl)pyrrole monosulphonic acid is dissolved in 100 ccs. of hot .water and the solution is added to 1000 cos. of the developing solution vused in Example 1.
Whena photographic element containing reducible silver salts is developed in,this solution a, clear greenish-blue dye image is produced together with metallic silver.
Example 3 1.0 gram of the ammonium salt of 2:4-diphenylpyrrole monosulphonic acid is dissolved in a mixture of 50 ccs. of water and 50 ccs. of acetone. A further 50 cos. of acetone are added to the solutionand the resulting mixture is added to 1000 ccs. of a developer of the following composition:
Crystalline sodium sulphite grams 15.0 Asymmetric diethyl p-phenyl-enediamine sulphate "grams" 3.0 Anhydrous sodium carbonate do 40.0 Potassium bromide do 0.5 Water to ccs. 1,000
A photographic element containing a developable silver halidev imageis treated with the above solution and a bright blue dye image is obtained together with the silver image.
Example 5 To 1000 ccs. of the developing solution used in Example 1 thereis added 100 ccs. of acetone and the resulting mixture is employed as a developer for a photographic element containing a ducible silver salts is developed in this solution a bright greenish-blue dye image is produced together with metallic silver. The silver may be reducible silver salt and also containing 2-phenyl- 4-(2-chlorophenyl) pyrrole in the form of a fine uniform dispersion. A bright greenish-blue dye image is obtained along with the silver image.
Photographic elements containing other color formers are developed in the developing solution used in Example 5. The color of the dye image obtained is shown in the table below:
Exall liple Color Former Color of image 6 B-benzoylamino-zf-i-dipbenylpyrrole.... Blue. 7 2-phe nyl-4(Pmethoxypheny )pyrrole Do. 8 2:4-dipheny pyrrole Do. 9 2-phenyl-4-(p-bromophenyl)pyrrole.. Do. 10 2-phenyl-4-(a-naphthyl) pyrrole Greenish-blue.
I claim: I,
1. A process for the production of a photographic dyestufi image which comprises developing a photographic element containing a reducible silver salt image with an aromatic primary amino color developing agent in the presence of a substituted 2 l-diarylpyrrole of the formula where R and R stand for aryl radicals and R stands for a member of the group consisting of hydrogen, aryl, alkyl, alkylamino, benzylideneamino, and acylamino radicals.
2. A photographic element bearing an emulsion layer containing a light-sensitive material and a color former comprising a 2:4-diarylpyrrole of the formula where R and R stand for aryl radicals and R stands for a member of the group consisting of hydrogen, aryl, alkyl, alkylamnio, benzylideneamino, and acylamino radicals.
3. A photographic element bearinga light-senwhere R and R stand for aryl radicals and R stands for a member of the group consisting of hydrogen, aryl, alkyl, alkylamino, benzylideneamino, and acylamino radicals. r
4'. A photographic developing solution containing an aromatic primary amino color developing agent and a color former comprising a substituted 2:4-diarylpyrrole of the formula Ru C Rm where R and R stand for ar yl radicals and R stands for a member of the group consisting of hydrogen, aryl, alkyl, alkylamino, benzylideneamino, and acylamino radicals.
DOUGLAS WILLIAM STAMNEERS.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB16705/42A GB562960A (en) | 1942-11-25 | 1942-11-25 | Production of coloured photographic images |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2396396A true US2396396A (en) | 1946-03-12 |
Family
ID=10082181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US510373A Expired - Lifetime US2396396A (en) | 1942-11-25 | 1943-11-15 | Production of colored photographic images |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US2396396A (en) |
| GB (1) | GB562960A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3245787A (en) * | 1959-11-13 | 1966-04-12 | Gevaert Photo Prod Nv | Production of color photographic images |
| EP0487111A1 (en) * | 1990-11-22 | 1992-05-27 | Fuji Photo Film Co., Ltd. | A novel color-forming coupler and a silver halide color photographic material containing the same |
| EP0488109A1 (en) * | 1990-11-26 | 1992-06-03 | Fuji Photo Film Co., Ltd. | Use of a cyan dye-forming coupler in a silver halide colour photographic material and a silver halide color photographic material containing the same |
-
1942
- 1942-11-25 GB GB16705/42A patent/GB562960A/en not_active Expired
-
1943
- 1943-11-15 US US510373A patent/US2396396A/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3245787A (en) * | 1959-11-13 | 1966-04-12 | Gevaert Photo Prod Nv | Production of color photographic images |
| EP0487111A1 (en) * | 1990-11-22 | 1992-05-27 | Fuji Photo Film Co., Ltd. | A novel color-forming coupler and a silver halide color photographic material containing the same |
| JPH04188137A (en) * | 1990-11-22 | 1992-07-06 | Fuji Photo Film Co Ltd | New coloring matter forming coupler and silver halide color photosensitive material containing it |
| US5260181A (en) * | 1990-11-22 | 1993-11-09 | Fuji Photo Film Co., Ltd. | Color-forming coupler and a silver halide color photographic material containing the same |
| JP2699024B2 (en) | 1990-11-22 | 1998-01-19 | 富士写真フイルム株式会社 | Novel dye-forming coupler and silver halide color photographic light-sensitive material containing the coupler |
| EP0488109A1 (en) * | 1990-11-26 | 1992-06-03 | Fuji Photo Film Co., Ltd. | Use of a cyan dye-forming coupler in a silver halide colour photographic material and a silver halide color photographic material containing the same |
| JPH04190347A (en) * | 1990-11-26 | 1992-07-08 | Fuji Photo Film Co Ltd | New pigment formation coupler and silver halogenide color photosensitive material containing this coupler |
| US5227287A (en) * | 1990-11-26 | 1993-07-13 | Fuji Photo Film Co., Ltd. | Color-forming coupler and a silver halide color photographic material containing the same |
| JP2671058B2 (en) | 1990-11-26 | 1997-10-29 | 富士写真フイルム株式会社 | Novel dye-forming coupler and silver halide color photographic light-sensitive material containing the coupler |
Also Published As
| Publication number | Publication date |
|---|---|
| GB562960A (en) | 1944-07-24 |
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