US2269481A - Production of colored photographic images - Google Patents

Production of colored photographic images Download PDF

Info

Publication number
US2269481A
US2269481A US286281A US28628139A US2269481A US 2269481 A US2269481 A US 2269481A US 286281 A US286281 A US 286281A US 28628139 A US28628139 A US 28628139A US 2269481 A US2269481 A US 2269481A
Authority
US
United States
Prior art keywords
mono
malonic acid
color
photographic
groups
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
Application number
US286281A
Inventor
Reindorp John Hubert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ilford Imaging UK Ltd
Original Assignee
Ilford Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ilford Ltd filed Critical Ilford Ltd
Application granted granted Critical
Publication of US2269481A publication Critical patent/US2269481A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups

Definitions

  • This invention relates to the production of colored photographic images by color development.
  • a colored image may be formed simultaneously with the silver image obtained by developing a silver halide emulsion with an aromatic amino developing agent if a substance known as a color former is present, for example, in the developing solution or in the silver halideemulsion.
  • the colored image may be revealed by bleaching out the silver image with Farmer's Reducer or other photographic bleaching agent.
  • a further object of the invention is to provide a methodof producing color photographic images with the aid of such color formers and a still further object is to provide light sensitive silver halide photographic materials containing 1 the new color formers.
  • the color-former employed is a malonic acid mono-ester mono-amide i. e. an organic compound of the general formula:
  • R1 and R2 represent hydrogen atoms or alkyl, aryl, aralkyl or heterocyclic groups (although they do not necessarily represent the same atoms or groups) or they represent groups linked together as a single cyclic grouping
  • R3 represents an alkyl, aryl or aralkyl group.
  • R1 may be a hydrogen atom, a methyl, ethyl, propyl or other alkyl group, a phenyl or other aryl group, a benzyl or other aralkyl group, a thiazole, thiazoline, oxazole, oxazoline, slenazole, selenazoline, pyridine, quincline, indolenine, diazine (e. g.
  • R2 may also be a hydrogen atom or any of the above mentioned groups although in any one compound it is not necessarily the same as 131'. Further, R1 and R1. may together form a single cyclic grouping, for example, a
  • R3 may be, for example, a methyl ethyl, propyl or butyl group, a phenyl group or a benzyl group.
  • the groups R1, R2 and R3 may themselves be substituted, e. g. by halogen atoms, by alkyl, aryl, aralkyl and other hydrocarbon groups, or by nitro groups, hydroxy groups, amino groups,'substi-- tuted amino groups, alkoxy groups or carbethoxy alkyl groups. Those compounds which contain substituted alkoxy groups yield, in general, colors of especial brilliance.
  • the preferred compounds for use according to the present invention are compounds of the type described above where R1 is a hydrogen atom and R2 is a substituted or unsubstituted phenyl group, suitable substituents in the phenyl group being halogen atoms or nitro, hydroxy, alkoxy or amino groups.
  • Typical compounds of this type are malonis acid mono ethyl ester mono-oanisidide and malonic acid mono ethyl .ester mono-o-chloranilide.
  • the compounds to be used as color formers in accordance with the invention. may be prepared by any suitable method.
  • a convenient method is to condense a compound of the type XCOCH2--COOR3 where R3 has the meaning assigned to it above and X is a halogen atom or an alkoxy group with a compound of the type Nil R. where R1 and R2 have the meanings assigned to them above.
  • malonic acid mono ethyl ester mono-'o-anisidide may be prepared by condensing malonic acid monoethylester mono acid chloride or malonic acid diethyl ester with o-anisidine.
  • Malonic acid mono ethyl ester mono-o-chloranilide may be prepared by a similar condensation using o-chloraniline instead of o-anisidine.
  • the color-formers of the invention may be "incorporated in the developing solution or in the photographic silver halide emulsion. In general, they are very insoluble in water and have little tendency to diffuse from one layer to another when incorporated in the emulsion layers of a multi-layer film or to diffuse into processing baths. Moreover, the compounds show a good resistance to the bleaching action of the sulphites frequently included in developing compositions.
  • Suitable aromatic amino compounds which may be employed as the developers in conjunction with the color-formers of this invention are derivatives of p-phenylene diamines and particularly of the asymmetric dialkyl-p-phenylene diamines, e. g. p-aminodimethylaniline, p-aminodiethylaniline and p-aminodibutylaniline.
  • developing agents which may be used include pphenylene-diamine itself, p-methylaminoaniline, p-ethylaminoaniline and p-aminophenol, N.N-diethyl-o-phenylene-diamine, chloro-p-phenylene diamine, 1.2.5-toluylenediamine, -2-amino-5-.diethyl-aminotoluene, N-p-aminophenylpiperidine, N methyl-N-hydroxyethyl-p-phenylenediamine, N-butyl-N-hydroxyethyl-p-phenylenediamine, 2- amino 5 (N-p-hydroxyethyl-Nbutyl) aminotoluene and its dihydrochloride and u-vdihydroxypropyl-p-phenylene diamine.
  • aromatic amino-developing agents may be used in the form of their salts, which may be either in organic or organic.
  • the salts are in general more stable than the free bases.
  • suitable salts mention is made of the hydrochlorides, sulfates and acetates.
  • a suitable development time, using this solution, is two minutes, at a temperature of 65 F.
  • Developing solution A when including this compound and used for the development of photographic silver halide images, produces a brilliant yellow image together with the silver image.
  • EXAMPLE 6 This example illustrates the incorporation of the color-formers of this invention in emulsion layers. 20 cos. of 1% solution in ethylene glycol mono-methyl ether of malonic acid mono ethyl ester mono-o-anisidide were added to 25 cos. of aqueous solution of gelatin and the mixture added to 50 cos. of a melted photographiMGa'slight emulsion containing approximately gms. of silver halide, principally silver chloride, per
  • emulsion thus prepared-was coated on'a paper support and dried.
  • the emulsion coated paper was exposed under a negative and was then developed with a developing solution of the constitution of Developing solution A excluding the color former but including an equivalent quantity'of the water miscible liquid such as ethyl alcohol or ethylene glycol mono methyl ether.
  • a brilliant yellow image was produced together with the silver image.
  • the dye image may be revealed by bleaching out the silver image with Farmer's Reducer or other known photo'- graphic bleaching agent.
  • color formers which may be prepared and used according to this invention:
  • the mono-p-cara camera or behind a photographic negative image may be applied to the residual silver halide left when an initial reduced silver image has been dissolved away as in the reversal process of development; or it may be applied to a developed photographic image in metallic silver which has been fixed by the removal of unchanged silver halide, and subsequently converted to a developable silver salt by means of known photographic bleaching agents.
  • the residual silver halide and the silver salt respectively may be made developable by the action of light or in any other way, e. g. by treatment with sodium arsenite.
  • the production of colored images by means of the color formers of this invention may be applied to colloid layers sensitised by bichromate.
  • the color formers may be incorporated in colloid layers (e. g. gelatin, gum arabic or albumin), the layers exposed, the unexposed colloid removed, e. g. by treatment with hot water, and the color developed in the exposed portions by treatment with p-nitro'so-dialkyl-aniline or its derivatives.
  • a photographic color forming developer which comprises an aromatic amino developing compound and a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
  • a photographic color forming developer which comprises an aromatic amino developing compound and a color former of the general formula:
  • R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups
  • R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
  • a photographic color forming developer which comprises an asymmetric di-alkyl-p-phenylene diamine and a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
  • a method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with an aromatic amino developing agent in the presence of a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
  • a method of producing a colored image in a silver halide emulsion which comprises developing the emulsion withan aromatic amino developing agent in the presence of a color former of the general formula:
  • R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups
  • R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
  • a method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with .an asymmetrical dialkyl-p-phenylene diamine in the presence of a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
  • a method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with a developing solution which contains an aromatic amino developing agent and a malonic acid mono-ester monoamide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
  • R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups
  • R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
  • R is an aromatic hydrocarbon radical containing an alkoxy group
  • R" is a lower alkyl group
  • a photographic color forming developer comprising an aromatic amino developing compound and the mono-o-anis-idicle of malonic acid ethyl ester.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Patented Jan. 13, 1942 PRODUCTION O FCOLORED PHOTOGRAPHIC WAGES John Hubert Reindorp, Ilford, England, assignor to Ilford Limited, Ilford, Essex, England, a
British company No Drawing. Application July 24, 1939, Serial No. 286,281. In Great Britain August 3, 1938 13 Claims.
This invention relates to the production of colored photographic images by color development.
It is known that a colored image may be formed simultaneously with the silver image obtained by developing a silver halide emulsion with an aromatic amino developing agent if a substance known as a color former is present, for example, in the developing solution or in the silver halideemulsion. The colored image may be revealed by bleaching out the silver image with Farmer's Reducer or other photographic bleaching agent.
It is an object of this invention to provide a new range of color formers. A further object of the invention is to provide a methodof producing color photographic images with the aid of such color formers and a still further object is to provide light sensitive silver halide photographic materials containing 1 the new color formers. 1
Other objects of the invention will appear hereinafter.
According (to the present invention in a process of color development in which a silver halide photographic emulsion is developed with an aromatic amino compound as a developer in the presence of a color-former, the color-former employed is a malonic acid mono-ester mono-amide i. e. an organic compound of the general formula:
where R1 and R2 represent hydrogen atoms or alkyl, aryl, aralkyl or heterocyclic groups (although they do not necessarily represent the same atoms or groups) or they represent groups linked together as a single cyclic grouping, and R3 represents an alkyl, aryl or aralkyl group. Thus, for example, R1 may be a hydrogen atom, a methyl, ethyl, propyl or other alkyl group, a phenyl or other aryl group, a benzyl or other aralkyl group, a thiazole, thiazoline, oxazole, oxazoline, slenazole, selenazoline, pyridine, quincline, indolenine, diazine (e. g. pyrimidine, and quinazoline) thiodiazole group, or a substituted or unsubstituded polycyclic group such as the benzthiazole, naphthathiazole and anthrathiazole groups, R2 may also be a hydrogen atom or any of the above mentioned groups although in any one compound it is not necessarily the same as 131'. Further, R1 and R1. may together form a single cyclic grouping, for example, a
' dolegroup. R3 may be, for example, a methyl ethyl, propyl or butyl group, a phenyl group or a benzyl group.
The groups R1, R2 and R3 may themselves be substituted, e. g. by halogen atoms, by alkyl, aryl, aralkyl and other hydrocarbon groups, or by nitro groups, hydroxy groups, amino groups,'substi-- tuted amino groups, alkoxy groups or carbethoxy alkyl groups. Those compounds which contain substituted alkoxy groups yield, in general, colors of especial brilliance.
The preferred compounds for use according to the present invention are compounds of the type described above where R1 is a hydrogen atom and R2 is a substituted or unsubstituted phenyl group, suitable substituents in the phenyl group being halogen atoms or nitro, hydroxy, alkoxy or amino groups. Typical compounds of this type are malonis acid mono ethyl ester mono-oanisidide and malonic acid mono ethyl .ester mono-o-chloranilide.
The compounds to be used as color formers in accordance with the invention. may be prepared by any suitable method. A convenient method is to condense a compound of the type XCOCH2--COOR3 where R3 has the meaning assigned to it above and X is a halogen atom or an alkoxy group with a compound of the type Nil R. where R1 and R2 have the meanings assigned to them above. Thus, for example, malonic acid mono ethyl ester mono-'o-anisididemay be prepared by condensing malonic acid monoethylester mono acid chloride or malonic acid diethyl ester with o-anisidine. Malonic acid mono ethyl ester mono-o-chloranilide may be prepared by a similar condensation using o-chloraniline instead of o-anisidine.
The color-formers of the invention may be "incorporated in the developing solution or in the photographic silver halide emulsion. In general, they are very insoluble in water and have little tendency to diffuse from one layer to another when incorporated in the emulsion layers of a multi-layer film or to diffuse into processing baths. Moreover, the compounds show a good resistance to the bleaching action of the sulphites frequently included in developing compositions.
Suitable aromatic amino compounds which may be employed as the developers in conjunction with the color-formers of this invention are derivatives of p-phenylene diamines and particularly of the asymmetric dialkyl-p-phenylene diamines, e. g. p-aminodimethylaniline, p-aminodiethylaniline and p-aminodibutylaniline. Other developing agents which may be used include pphenylene-diamine itself, p-methylaminoaniline, p-ethylaminoaniline and p-aminophenol, N.N-diethyl-o-phenylene-diamine, chloro-p-phenylene diamine, 1.2.5-toluylenediamine, -2-amino-5-.diethyl-aminotoluene, N-p-aminophenylpiperidine, N methyl-N-hydroxyethyl-p-phenylenediamine, N-butyl-N-hydroxyethyl-p-phenylenediamine, 2- amino 5 (N-p-hydroxyethyl-Nbutyl) aminotoluene and its dihydrochloride and u-vdihydroxypropyl-p-phenylene diamine. These aromatic amino-developing agents may be used in the form of their salts, which may be either in organic or organic. The salts are in general more stable than the free bases. As examples of suitable salts mention is made of the hydrochlorides, sulfates and acetates.
In the succeeding examples, the following solution is given by way of example as illustrating the nature of developing solutions which may be employed embodying a color former in accordance with the invention.
Developing solution A Diethyl-p-phenylenediaminehydrochloride grams 1 Sodium carbonate (crystals) NazCOslOI-IzO 80 Sodium sulphite (crystals) Na2SO37H2O dO 12.5 Color former solution (1% or saturated solution, whichever is weaker) ccs 100 Water to make 1itre 1 The color former is dissolved in a suitable water-miscible solvent such as ethyl alcohol or ethylene glycol mono-methyl ether. The sodium sulphite may be omitted if desired.
A suitable development time, using this solution, is two minutes, at a temperature of 65 F.
Th following specific examples illustrate the method of production of the new color formers, and their use:
EXAMPLE 1 Malom'c acid mono ethyl ester mono-o-anisidide cooled solution was filtered.
The filtrate was then diluted to four times its volume with petroleum ether and cooled in a freezing mixture, whereupon the malonic acid mono ethyl ester mono-o-anisidide separated out. M. P. 63-65 C.
Developing solution A, when including this compound and used for the development of photographic silver halide images, produces a brilliant yellow image together with the silver image.
EXAMPLE 2 Melanie acid mono ethyl ester mono-flnaphthalidc EXAMPLE 3 Melanie acid mono ethyl ester mono-m- Y nitram'lide 10 cos. of diethylmalonate and 4.08 gms. of mnitraniline were heated together in an oil bath for three hours at 130-140 C.
The excess diethylmalonate was then distilled off in vacuo and the residue was warmed with 60 ccs. of dry ethyl alcohol. The mixture was then cooled in a freezing mixture and filtered. The filtrate was evaporated on a water bath to remove the ethyl alcohol and Water was added. The mixture was then cooled in ice and filtered. The residue was then boiled up with benzene and filtered hot; the filtrate was evaporated to 10 ccs. and allowed to cool, whereupon yellow crys tals of malonic acid mono ethyl ester mono-mnitranilide separated. M. P. 48 C.
Developing solution A when including this compound and used for the development of photographic silver h-alide images produces a bright yellow image together with the silver ima e.
EXAMPLE 4 Malonz'c acid mono ethyl ester monoo-hydroxyanilide Q- NH- 00- cm 00- 002m 5.45 gms. of o-amino-phenol and 40 gms. of diethylmalonate were heated in an oil bath, for three hours, at C. On cooling, a brown solid, M. P. 106 C. separated and this was recrystallised from benzene. Developing solution A, when including this compound and used for the development of photographic silver halide images produces a deep green image together with the silver image.
EXAMPLE 5 1-w-carbethoryacetylamino benzthiazole o- Nllc 0 cmo o (,n,
4.5 gms. of l-amino-benzthiazole were dissolved by warming in 200 ccs. of xylene and the solution was slowly added to a solution of 9.6 gms. of diethylmalonate in 15 ccs. of xylene and contain ing two drops of pyridine, the addition of the 1- amino-benzthiazole being effected over a period of about thirty minutes.
During this process the solutions were maintained at boiling and about 100 cos. of the xylene was removed. On cooling the products, a yellow solid separated, which on recrystallisation from ethyl alcohol had a melting point of 180 C. Developing solution A when including this compound and used for the development of photographic silver halide images produces an orangebrown image together with the silverimage.
EXAMPLE 6 This example illustrates the incorporation of the color-formers of this invention in emulsion layers. 20 cos. of 1% solution in ethylene glycol mono-methyl ether of malonic acid mono ethyl ester mono-o-anisidide were added to 25 cos. of aqueous solution of gelatin and the mixture added to 50 cos. of a melted photographiMGa'slight emulsion containing approximately gms. of silver halide, principally silver chloride, per
pound weight of emulsion. The emulsion thus prepared-was coated on'a paper support and dried. The emulsion coated paper was exposed under a negative and was then developed with a developing solution of the constitution of Developing solution A excluding the color former but including an equivalent quantity'of the water miscible liquid such as ethyl alcohol or ethylene glycol mono methyl ether. A brilliant yellow image was produced together with the silver image.
In each of the above examples the dye image may be revealed by bleaching out the silver image with Farmer's Reducer or other known photo'- graphic bleaching agent.
In addition to the specific color formers described above, the following are examples of color formers which may be prepared and used according to this invention:
Malonic acid mono ethyl ester mono-p-anisidide Malonic acid mono ethyl ester mono-p-nitroanilide Malonic acid mono ethyl ester mono-anaphthalide l-w-carbethoxy acetylamino-S ethoxy benzthiazole Malonic acid mono ethyl ester mono anilide Malonic acid mono ethyl ester mono-o-nitroanilide Malonic acid mono ethyl ester bethoxy-anilide N.N'-di-carbethoxyacetyl benzidine 1-w-carbethoxyacetylamino-2-hydroxy 4:5 dimethylbenzene Malonic acid di-o-hydroxy-p-nitroanilide Malonic acid mono ethyl ester mono-o-chloranilide The process of development employing the color formers in accordance with the present invention may be applied either to a latent image in an emulsion of a silver halide which has been exposed to the action of light, for example, in
mono-p-cara camera or behind a photographic negative image; or it may be applied to the residual silver halide left when an initial reduced silver image has been dissolved away as in the reversal process of development; or it may be applied to a developed photographic image in metallic silver which has been fixed by the removal of unchanged silver halide, and subsequently converted to a developable silver salt by means of known photographic bleaching agents. In the last two cases the residual silver halide and the silver salt respectively may be made developable by the action of light or in any other way, e. g. by treatment with sodium arsenite.
The production of colored images by means of the color formers of this invention may be applied to colloid layers sensitised by bichromate. Thus the color formers may be incorporated in colloid layers (e. g. gelatin, gum arabic or albumin), the layers exposed, the unexposed colloid removed, e. g. by treatment with hot water, and the color developed in the exposed portions by treatment with p-nitro'so-dialkyl-aniline or its derivatives.
I claim:
1. A photographic color forming developer which comprises an aromatic amino developing compound and a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
2. A photographic color forming developer which comprises an aromatic amino developing compound and a color former of the general formula:
wherein R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups, and R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
3. A photographic color forming developer which comprises an asymmetric di-alkyl-p-phenylene diamine and a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
4. A method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with an aromatic amino developing agent in the presence of a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
5. A method of producing a colored image in a silver halide emulsion which comprises developing the emulsion withan aromatic amino developing agent in the presence of a color former of the general formula:
ncoomcoom wherein R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups, and R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
6. A method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with .an asymmetrical dialkyl-p-phenylene diamine in the presence of a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
7. A method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with a developing solution which contains an aromatic amino developing agent and a malonic acid mono-ester monoamide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
8. A light sensitive silver halide photographic emulsion containing a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
9. A photographic element bearing at least one light sensitive silver halide emulsion layer containing a color former of the general formula:
wherein R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups, and R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
10. A light sensitive silver halide emulsion containing as a color former a compound of the general formula:
wherein R is an aromatic hydrocarbon radical containing an alkoxy group, and R" is a lower alkyl group.
11. A light sensitive silver halide emulsion containingas a color former the mono-o-anisidide of malonic acid ethyl ester.
12. A photographic color forming developer comprising an aromatic amino developing compound and the mono-o-anis-idicle of malonic acid ethyl ester.
13. The process which comprises developing a photographic element bearing silver halide image in the presence of the mono-o-anisidide of malonic acid ethyl ester with a color coupling aromatic amino developing agent containing an unsubstituted amino group.
JOHN HUBERT REINDORR- CERTIFICATE OF commoners. Patent No. 2,269,l;81. January 1 191;.2.
JOHN HUBERT REINDORP.
It is hereby, certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page l', second column, line 20, for "malonis" reed malonio--; page 2, second column, line 5, in the for-mule, for "NC" read --NH--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 5rd. day of March, A. D.- 19)+2.
Henry Van Arsdale, (Seal) Acting Commis sioner of Patents.
US286281A 1938-08-03 1939-07-24 Production of colored photographic images Expired - Lifetime US2269481A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB22987/38A GB518017A (en) 1938-08-03 1938-08-03 Improvements in or relating to the colour-development of silver halide photographic emulsions

Publications (1)

Publication Number Publication Date
US2269481A true US2269481A (en) 1942-01-13

Family

ID=10188261

Family Applications (1)

Application Number Title Priority Date Filing Date
US286281A Expired - Lifetime US2269481A (en) 1938-08-03 1939-07-24 Production of colored photographic images

Country Status (2)

Country Link
US (1) US2269481A (en)
GB (1) GB518017A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2441491A (en) * 1944-05-12 1948-05-11 Ilford Ltd Cyanacetylamino phenol color formers for color photography
US2533185A (en) * 1947-10-22 1950-12-05 Gen Aniline & Film Corp Alkyl malonamates as azo coupling components in diazotype layers
US2645578A (en) * 1949-01-22 1953-07-14 Harris Seybold Co Lithograph-plate preparation
DE1124356B (en) * 1960-04-28 1962-02-22 Eastman Kodak Co Process for photographic color developing
US4157916A (en) * 1976-07-13 1979-06-12 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4560646A (en) * 1983-11-23 1985-12-24 Ciba Geigy Ag Protected developing agents

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2441491A (en) * 1944-05-12 1948-05-11 Ilford Ltd Cyanacetylamino phenol color formers for color photography
US2533185A (en) * 1947-10-22 1950-12-05 Gen Aniline & Film Corp Alkyl malonamates as azo coupling components in diazotype layers
US2645578A (en) * 1949-01-22 1953-07-14 Harris Seybold Co Lithograph-plate preparation
DE1124356B (en) * 1960-04-28 1962-02-22 Eastman Kodak Co Process for photographic color developing
US4157916A (en) * 1976-07-13 1979-06-12 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4560646A (en) * 1983-11-23 1985-12-24 Ciba Geigy Ag Protected developing agents

Also Published As

Publication number Publication date
GB518017A (en) 1940-02-15

Similar Documents

Publication Publication Date Title
US2213986A (en) Production of colored photographic images
US2342546A (en) Production and use of dyestuffs
US2323503A (en) Methylene bis-azoles
US2312040A (en) Production of colored photographic images by color development and composition therefor
US2323504A (en) Preparation of omega-acyl-azoles
US3482971A (en) Scavengers for oxidized developing agent
US3615505A (en) Silver halide emulsion containing 2-pyrazolin-5-one color coupler
US2412700A (en) Thioglycolic amides
US2937089A (en) Supersensitized photographic emulsions containing sulfonated compounds
US2269481A (en) Production of colored photographic images
US2334495A (en) Color photography
US2331326A (en) Production of colored photographic images
US2186736A (en) Coupling compounds for color forming development
US3222176A (en) Photographic colour images from amino substituted phenols
US2333106A (en) Color photography
US2282116A (en) Photographic element
US2359274A (en) Processes of color photography using azole color formers
US2184303A (en) Photographic color-forming developer and emulsion
US2448939A (en) Thioglycolic amide couplers
US2993791A (en) Color couplers containing long chain alkylaminoisophthalicester groups
US2441491A (en) Cyanacetylamino phenol color formers for color photography
DE885197C (en) Process for the production of purple photographic images in halogen-gelatin emulsion layers by color-forming development
US2326497A (en) Water-soluble nitrogen-containing heterocyclic compound
US2177635A (en) Photographic emulsion
US2500487A (en) Yellow diffusion-fast color formers of the benzimidazole class