US2982649A - Production of colored photographic images - Google Patents

Production of colored photographic images Download PDF

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Publication number
US2982649A
US2982649A US719994A US71999458A US2982649A US 2982649 A US2982649 A US 2982649A US 719994 A US719994 A US 719994A US 71999458 A US71999458 A US 71999458A US 2982649 A US2982649 A US 2982649A
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Prior art keywords
amino
methoxy
sulphonamide
acetyl
benzene
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US719994A
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Tavernier Bernard Hippoliet
Desmit Marcel Leon
Cat Arthur Henri De
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Gevaert Photo Producten NV
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Gevaert Photo Producten NV
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32Colour coupling substances
    • G03C7/36Couplers containing compounds with active methylene groups

Definitions

  • the present invention relates to a process for the manufacture of colored photographic images by color development in the presence of a color coupler, to photographic developers which contain such color coupler and to photographic images obtained according to this process.
  • Yellow colored images are usually obtained by development in the presence of compounds which contain an active methylene group, particularly acylacetanilide derivatives.
  • acylacetanilide derivatives those which are substituted in their anilide part by a sulphonamide group are known to have the property of being highly soluble in the developer whilst the resulting dyestulfs nevertheless have no tendency to bleed out.
  • these objects are accomplished by developing a reducible silver salt irnage with an aromatic amino developing agent in the presence of an aliphatic, aromatic or heterocyclic acyl acetarylide, thearylide part of which is substituted in 2- position by an alkoxy group and in 5-position by an alkyl or aryl sulphonamide group.
  • the presence during color development of color couplers according to the present invention may arise from adding to the developer a compound which differs from the color coupler only because in the active CH -group one or two hydrogen atoms are replaced by a group capable of splitting ofi either before development occurs by the action'of the alkali in the developing solution or during the color-development.
  • aromatic amino compounds which according to our invention are used as developing agents, comprise mono-, diand tri-arnino aryl compounds, particularly N:N-dialkyl-paraphenylene diamines and derivatives such as N:N-dialkyl-N-sulphomethyl-para-phenylene diamines.
  • mono-amino developers amino-phenols, amino-cresols and their halogen derivatives, and also amino-naphthols may be mentioned.
  • An exposed photographicjfilrn strip coated with a silver halide emulsion layer is developedin a bath of the following composition:
  • Couplers l-6 prepared as described above l Water to 50 emf.
  • solution B is added to solution A and ter is added to the resultingsolution to 1,000 cmEr.
  • Photographic color developer containing pdiethylamino-aniline hydrochloride as anam'ino aromatic developing agent and a color coupler, whereby said coupler is 3.(benzoyl-acetyl-amino) -4-methoxy-benzene-phenyl-sulphonamide.
  • Photographic color developer containing p-diethylamino-aniline hydrochloride as an amino aromatic developing agent and a color coupler, whereby said coupler is 3 (acetyl-acetyl-amino)-4-methoXy-benzene:phenylsulphonamide.
  • Photographic color developer containing p-diethylamino-aniline hydrochloride as an amino aromatic developing agent and a color coupler, whereby said coupler is 3(thenoyl-acetyl-amino) 4-methoxy-benzene-phenylsulphonamide.
  • Photographic color developer containing p-diethylamino-aniline hydrochloride as an aromatic aminodeveloping agent and an acylacetanilide coupler selected from the group consisting .of v3(benzoyl-acetyl-amino)-4methoxy-benzene-n-butyl-sulphonamide, 3(benzoyl-acetyl-amino)-4-methoxy-benzene-phenyl-sulphonamide, 3(benzoylacetyl-amino)-4-methoxy-benzenc-p-methoxy phenyl-sulphonamide, .3 (acetyl-acetyl-amino)-4-mcthoxy benzenephenyl-sulphonamide, and 3(thenoyl-acetyl-amino.)'4- methoxy-benzene phenyl'sulphonamide.

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

Description

United States Patent F PRODUCTION OF COLORED PHOTOGRAPHIC IMAGES Bernard Hippoliet Tavernier and Marcel Lon Desmit, Antwerp, and Arthur Henri De Cat, lldortsel-Antwerp, Belgium, assignors to Gevaert Photo-Producten N.V., Mortsel, Belgium, a Belgian company No Drawing. Filed Mar. 10, 1953, Ser. No. 719,994
6 Claims. c1. es-ss The present invention relates to a process for the manufacture of colored photographic images by color development in the presence of a color coupler, to photographic developers which contain such color coupler and to photographic images obtained according to this process.
It is known to obtain a colored photographic image by developing a reducible silver salt image in the presence of a color coupler, i.e. a compound which during development couples with the oxidation product of the developing agent and forms a dyestuff which precipitates onto the developed silver grains.
Yellow colored images are usually obtained by development in the presence of compounds which contain an active methylene group, particularly acylacetanilide derivatives.
Among the acylacetanilide derivatives, those which are substituted in their anilide part by a sulphonamide group are known to have the property of being highly soluble in the developer whilst the resulting dyestulfs nevertheless have no tendency to bleed out.
It is an object of the present invention to provide a new process of color development, more particularly in the presence of a color coupler, which is more reactive than the known sulphonamido substituted acylacetanilides. It is another object of the present invention to provide a new color developer containing such a color coupler. It is a further object of the present invention to provide new colored photographic images obtained by such process. Still further objects will'appear from the description hereinafter.
According to the present invention, these objects are accomplished by developing a reducible silver salt irnage with an aromatic amino developing agent in the presence of an aliphatic, aromatic or heterocyclic acyl acetarylide, thearylide part of which is substituted in 2- position by an alkoxy group and in 5-position by an alkyl or aryl sulphonamide group.
These compounds may be obtained as follows: 1 mol of a 3-acetamino-4-alkoXy-benzene sulphochloride, for instance the 4-methoxy compound described by K. Child, J. Chem. Soc. (1932), 715/720, is added at 40-50 C. to 2 mols of a primary amine dissolved in dioxane. After refluxing for ninety minutes the precipitate obtained on cooling is sucked off, washed with water and recrystallized.
In this way the following can be prepared:
3 acetamino 4 methoxy benzene n butyl sulphonamide, melting at 114115 C., 3 acetamino 4' methoxy benzene phenyl sulphonamide, melting at 198-200 C., 3 acetamino 4 methoxy benzene.- p -.methoxy phenyl-sulphonamide, meltingat 162-164 C.
2,982,649 Patented May 2,1961
ice
In this way the following can be obtained:
3-amino-4-methoxy-n-butyl-sulphonamide, melting at 99- 3-arnino-4-methoxy-phenyl-sulphonamide, melting at 139- 140 C.,
3 amino 4 methoxy p methoxyphenyl sulphonamide, melting at 135-136 C.
These compounds are refluxed with an excess oi betaketo ester. The precipitate obtained on cooling is sucked off, washed with a diluted acid and recrystallized until white crystals are obtained.
In this way the following can be prepared:
(1) 3(benzoyl acetyl amino) 4 methoxy benzenen-butyl-sulphonamide, melting at 95-97 C.,
(2) 3(benz'oy1 acetyl amino) 4 methoxy benzenep-methoxyphenyl-sulphonamide, melting at 179-180" (3) 3(benzoyl acetyl amino) 4 methoxy benzenephenyl-sulphonamide, melting at -161 C.,
(4) 3(acetyl acetyl amino) 4 methoxy benzenephenyl-sulphonamide, melting at 196l97 C.,
(5) 3(alpha thenoyl acetyl amino) 4 methoxybenzene-phenyl-sulphonamide, melting at 200202 C.,
(6) 3(p methoxy benzoyl acetyl amino) 4- methoxy-benzene-phenyl-sulphonamide, melting at 194 C.
The presence during color development of color couplers according to the present invention may arise from adding to the developer a compound which differs from the color coupler only because in the active CH -group one or two hydrogen atoms are replaced by a group capable of splitting ofi either before development occurs by the action'of the alkali in the developing solution or during the color-development.
The aromatic amino compounds, which according to our invention are used as developing agents, comprise mono-, diand tri-arnino aryl compounds, particularly N:N-dialkyl-paraphenylene diamines and derivatives such as N:N-dialkyl-N-sulphomethyl-para-phenylene diamines. As mono-amino developers amino-phenols, amino-cresols and their halogen derivatives, and also amino-naphthols may be mentioned.
The following example serves to illustrate the invention without, however, limiting the scope thereof.
An exposed photographicjfilrn strip coated with a silver halide emulsion layer is developedin a bath of the following composition:
One of the couplers l-6 prepared as described above l Water to 50 emf.
Before use, solution B is added to solution A and ter is added to the resultingsolution to 1,000 cmEr. The
developed image is rinsed for thirty minutes and the? silver is bleached in the following bathz' fPotassium,ferricyanide aaabn nnma; 50
Water to 1,000 cmfi.
Sodium thiosulphate 250 g. Water to 1,000 cm.-'. and again rinsed for thirty minutes.
A yellow image is obtained.
We claim:
1. Process for producing a colored photographic-image by developing a reducible silver salt imagewith ,p-diethylamino-aniline hydrochloride as an aromatic amino developing agent in the presence of an acylacetanilide coupler, whereby said coupler is 3(benzoyl-acetyl-amino)- 4-methoxy-benzene-phenyl-sulphonamide.
2. Photographic color developer containing pdiethylamino-aniline hydrochloride as anam'ino aromatic developing agent and a color coupler, whereby said coupler is 3.(benzoyl-acetyl-amino) -4-methoxy-benzene-phenyl-sulphonamide.
3. Photographic color developer containing p-diethylamino-aniline hydrochloride as an amino aromatic developing agent and a color coupler, whereby said coupler is 3 (acetyl-acetyl-amino)-4-methoXy-benzene:phenylsulphonamide.
4. Photographic color developer containing p-diethylamino-aniline hydrochloride as an amino aromatic developing agent and a color coupler, whereby said coupler is 3(thenoyl-acetyl-amino) 4-methoxy-benzene-phenylsulphonamide.
5. Process for producing a colored photographic image by developing a reducible silver salt image with p-diethylamino-aniline hydrochloride as an aromatic amino developing agent in the presence of an acylacetanilide coupler selected from the group consisting of 3(benzoyl-acetyl-amino 4 methoxy-benzene-n-butyl-sulphonamide, 3- (benzoyl-acetyl-amino)- 14 .methoxy-benzene-phenyl-sulphonamide, .3- (.benzoyl-acetyl-amino) -4-methoxwbenzenep-methoXy-pheny1-sulphonamide, 3 (acetyl'acetyl-amino') 4-methoxy-benzene-phenyl-sulphonamide, and 3(thenoylacetyl-amino) -4-methoxy benzene-phenyl-sulphon amide.
6. Photographic color developer containing p-diethylamino-aniline hydrochloride as an aromatic aminodeveloping agent and an acylacetanilide coupler selected from the group consisting .of v3(benzoyl-acetyl-amino)-4methoxy-benzene-n-butyl-sulphonamide, 3(benzoyl-acetyl-amino)-4-methoxy-benzene-phenyl-sulphonamide, 3(benzoylacetyl-amino)-4-methoxy-benzenc-p-methoxy phenyl-sulphonamide, .3 (acetyl-acetyl-amino)-4-mcthoxy benzenephenyl-sulphonamide, and 3(thenoyl-acetyl-amino.)'4- methoxy-benzene phenyl'sulphonamide.
References Cited in the file of this-patent UNITED STATES PATENTS 2,271,238 Vittum et a1. Jan. 27, '1942 2,350,138 Weissberger May 30, 1944 2,407,210 Weissberger et a1 Sept. 3, 1946 2,596,755 Young et a1. May 13, 1952 2,694,718 Salminen et a1. Nov. 16, 1954

Claims (2)

  1. 5. PROCESS FOR PRODUCING A COLORED PHOTOGRAPHIC IMAGE BY DEVELOPING A REDUCIBLE SILVER SALT IMAGE WITH P-DIETHYLAMINO-ANILINE HYDROCHLORIDE AS AN AROMATIC AMINO DEVELOPING AGENT IN THE PRESENCE OF AN ACYLACETANILIDE COUPLER SELECTED FROM THE GROUP CONSISTING OF 3(BENZOYL-ACETYL-AMINO -4- METHOXY-BENZENE-N-BUTYL-SULPHONAMIDE, 3(BENZOYL-ACETYL-AMINO)- 4 -METHOXY-BENZENE-PHENYL-SULPHONAMIDE, 3-(BENZOYL-ACETYL-AMINO)-4-METHOXY-BENZENEP-METHOXY-PHENYL-SULPHONAMIDE, 3(ACETYL-ACETYL-AMINO)4-METHOXY-BENZENE-PHENYL-SULPHONAMIDE, AND 3(THENOYLACETYL-AMINO)-4-METHOXY-BENZENE-PHENYL-SULPHONAMIDE.
  2. 6. PHOTOGRAPHIC COLOR DEVELOPER CONTAINING P-DIETHYLAMINO-ANILINE HYDROCHLORIDE AS AN AROMATIC AMINO DEVELOPING AGENT AND AN ACYLACETANILIDE COUPLER SELECTED FROM THE GROUP CONSISTING OF 3(BENZOYL-ACETYL-AMINO)-4-METHOXY-BENZENE-N-BUTYL-SULPHONAMIDE, 3(BENZOYL-ACETYL-AMINO)-4-METHOXY-BENZENE-PHENYL-SULPHONAMIDE, 3(BENZOYLACETYL-AMINO)-4-METHOXY-BENZENE-P-METHOXY - PHENYL-SULPHONAMIDE, 3(ACETYL-ACETYL-AMINO)-4-METHOXY-BENZENEPHENYL-SULPHONAMIDE, AND 3(THENOYL-ACETYL-AMINO)-4METHOXY-BENZENE-PHENYL-SULPHONAMIDE.
US719994A 1958-03-10 1958-03-10 Production of colored photographic images Expired - Lifetime US2982649A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2271238A (en) * 1939-03-31 1942-01-27 Eastman Kodak Co Color forming compounds containing sulphonamide groups
US2350138A (en) * 1940-08-22 1944-05-30 Eastman Kodak Co Nondiffusing acylacetyl sulphonamide coupler
US2407210A (en) * 1944-04-14 1946-09-03 Eastman Kodak Co Color couplers
US2596755A (en) * 1948-01-13 1952-05-13 Eastman Kodak Co Aromatic color couplers containing mercaptan and hydroxyl groups
US2694718A (en) * 1951-12-05 1954-11-16 Eastman Kodak Co Sulfobenzamides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2271238A (en) * 1939-03-31 1942-01-27 Eastman Kodak Co Color forming compounds containing sulphonamide groups
US2350138A (en) * 1940-08-22 1944-05-30 Eastman Kodak Co Nondiffusing acylacetyl sulphonamide coupler
US2407210A (en) * 1944-04-14 1946-09-03 Eastman Kodak Co Color couplers
US2596755A (en) * 1948-01-13 1952-05-13 Eastman Kodak Co Aromatic color couplers containing mercaptan and hydroxyl groups
US2694718A (en) * 1951-12-05 1954-11-16 Eastman Kodak Co Sulfobenzamides

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