US3808007A - Diffusion-resistant purple color couplers for the preparation of photographic color pictures - Google Patents

Diffusion-resistant purple color couplers for the preparation of photographic color pictures Download PDF

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Publication number
US3808007A
US3808007A US00175703A US17570371A US3808007A US 3808007 A US3808007 A US 3808007A US 00175703 A US00175703 A US 00175703A US 17570371 A US17570371 A US 17570371A US 3808007 A US3808007 A US 3808007A
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United States
Prior art keywords
color
photographic
couplers
purple
diffusion
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Expired - Lifetime
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US00175703A
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English (en)
Inventor
E Meier
K Kuffner
W Schulte
H Glockner
F Nittel
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Agfa Gevaert AG
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Agfa Gevaert AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
    • C09B29/3652—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles
    • C09B29/366—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles containing hydroxy-1,2-diazoles, e.g. pyrazolone
    • 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
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

  • the water-insoluble couplers contain a diffusion-preventing radical, mostly bound by an acylamino grouping. According to known methods,
  • Such couplers are dispersed with the aid of wetting agents and if necessary oil formers into gelatin and in this form are added to the silver halide emulsion.
  • the Netherlands Patent No. 6,413,277 discloses anilinopyrazolone couplers wherein the diffusion-preventing radical is directly bound to the phenyl radical of the aniline group.
  • the couplers contain a sulfo group in the aniline radical.
  • Such couplers may be added to the emulsion in the form of the aqueous solution of an alkali salt.
  • R is H or one or several substituents, customary to -p q -p aaplqnss s c as l xl-ial sqxyrl a I Absorptions, maximum: 535 mu kylothio-, phenoxy-, halogen-, carboxy-, sulfo acidalkylsulfono-, carbalkoxy-, carbamido-, sulfofluorido-, cyano-, nitrogroups;
  • R is alkyl, aryl, O-alkyl, O-aryl, NH-alkyl, NH-aryl,
  • R contains particularly a diffusionpreventing group in the form of one or several straight, branched or cyclic hydrocarbon radicals with collectively at least eight carbon atoms;
  • R is H or a radical, separable in the developing, such as Cl, 1-1 or a substituted phenylazo group, as the case may be;
  • n l or 2.
  • novel purple components are advantageously distinguished over the known anilino-pyrazolone components in many respects. They contain an acylamino grouping which advantageously affects the photographic properties and by means of which the diffusionpreventing radical may be introduced in particular abundance.
  • the sulfo group enables the introduction of the components into the photographic emulsion without special dispersion steps and without the aid of special dispersing additives. In this manner. a high degree of dispersion is achieved with these couplers.
  • the sulfo group affects exactly in the aniline radical in the advantageous manner the spectral properties of the purple coloring substances: Undesired secondary absorptions, in comparison to the unsulfonated components, are lessened, and the position of the absorption maximum may be affected depending at which point in the aniline radicalthe sulfo group is introduced. This last-named advantage shows up less in the absorption.
  • the components of the invention may be. used both 60 and 1,134,329 and the commonly owned U.S. applicain the negative/positive process as well as in the reverse v tion Ser. No. 849,498 filed Dec. 8, 1969 by Hans Glockner, Ernst Meier and Walter Puschel.
  • couplers are made by reacting an amino anilino pyrazolone with a chloroformic acid ester.
  • suitable esters of the chloroformic acid are for instance the following: ethylester, 2'-hexylnonylester, hexadecylester, 4-bromobutylester; cyclohexylester, tetrahydrofurfurylester; phenylester, p-
  • nitrophenylester p-dodecylphenylester, n-pentadecylphenylester, 2,4-dichloro-6-tetradecylphenylester, ooctadecyloxy -phenylester, p-chloro-o-tetradecylphenylester; p-butylphenoxyethylester, 2-butyl-4-nonylphenylester, m-pentadecylphenoxyethylester, pdodecyloxyphenoxypropylester, 4 chloro-3-methyl-6- tetradecylphenoxypropylester.
  • couplers are then subjected in a known manner to a sulfonation process.
  • Sulfonation agents for example, are concentrated sulfuric acid or chlorosulfonic acid.
  • the sulfonation agent may be added to the unsulfonated coupler or also in reverse. Analytical investigation shows that the sulfonation preferably takes place in the aniline portion of the molecule. A sulfo group initially set in in the 4-position of the molecule (coupling point) is again separated in the working up.
  • 1f homogeneous components according to the present invention are to be prepared wherein the placing of the components of the sulfo groups is clear, one must start with defined intermediate sulfonation products with respect to the pyrazolone synthesis.
  • most of the known methods for the preparation of anilinopyrazolones fail.
  • the reaction of aniline sulfo acids with B,B,B-trialkoxypropionic acid esters well achieves its goal.
  • 3-anilino-pyrazolone-(5) of the general fonnula may be prepared by reacting a B,B,B-trialkoxy propionic acid alkyl ester of the general formula RQO7CCHQCOORI 7 R o with an aniline of the formula LII 8 and condensation of the intermediate productobtained with a hydrazine of the formula Il -NH NH2 5
  • R is alkyl, aralkyl, aryl, if necessary substituted by one or several alkyl-, alkoxy-, alkylthio-, phenoxy-, halogen-, carboxy-, sulfo acid-, alkylsulfonic, carbalkoxy-, carbamide-, su1fofluoride-, cyano-, nitro groups
  • R is 1-1 or one or several substituents such as an alkylalkoxy-, alkylthio-, halogen-, caboxy-, sulfo aeid
  • the B,B,B-trialkoxy propionic acid esters, used according to the invention, may also be designated chemically as semi-orthoesters of malonic acid.
  • a compound of this sort of B,B,B-triethoxypropionates is described by McElvain, Schroeder, Am. Soc. 71, 1949, pp. 44-45.
  • the correspondingtrimethoxy propionic acid ethyl ester is very stable in pure form and may be employed particularly well according to the invention.
  • chloraniline 2,4-dichloraniline, m-tadine, pdodecylaniline, m-nitroaniline, sulfanilic acid, 2-amino-4-nitrobenzene sulfonic acid, 2-nitro-4- aminobenzene sulfonic acid, 2-nitro-4-chlor-5- aminobenzene sulfonic acid.
  • the reaction of the aniline with the orthoester takes place at temperatures between 20 and 100C, preferably in the presence of glacial acetic acid.
  • the yields of the intermediate product obtained, B-alkoxy-B-anilino acryclic acid ester, are nearly quantitative. In most instances, a purification with hydrazine prior to the reaction is eliminated.
  • Suitable hydrazines for a pyrazone synthesis are, for example, phenyl hydrazine, m-chlorphenyl hydrazine, 2,4,6-trichlorophenyl hydrazine, p-nitrophenyl hydrazine, 2-nitro-4-trifluoromethylphenyl hyrdazine, 2- cetyloxyphenyl hydrazine, 4-hydrazino-phenylcetylfulfone, 4-chloro-5-hydrazino-phenylchloromethylsulfone, phenylhydrazine-m-sulfonic acid, ethyl-hydrazine, benzyl hydrazine, 2-chlorobenzyl hydrazine.
  • Nitro compound from Step 1 were introduced into 100 g SnCl '2H O with 200 ml HCl concentrated at 85l00C during stirring. The stirring was continued at 95C for another minutes after the completion of the reaction. The white precipitate was drawn off upon cooling and washed with percent BC]. The moist crude product was mixed with methanol and again drawn off. The free amine was obtained by dissolving in water/alkali and precipitating with an excess of glacial acetic acid.
  • a solution of the coupler was prepared in the customary manner in that it was suspended in methanol and mixed with thinned soda lye. This solution was added to a silver halide emulsion. Thereupon, it was poured ona carrier and dried. The photographic film obtained was illuminated under a stepped photometric absorption wedge and was subjected to a color negative developing process. The developing substance was N,- N-diethyl-3-methyl-p-phenylenediamine. Thereupon, the film was treated in a bleaching solution and in a fixing solution and dried. Obtained was a negative purple picture. Absorption maximum 540 mp.
  • the screened component was dissolved in water as lithium salt and incorporated in a green-sensitive negative emulsion.
  • the emulsion was poured as a partial layer of a multi-film negative material. Dried and pictorially illuminated with green light; after customary processing in a color negative process using 4-amino-3-methyl-N-ethyl-N- methane sulfonamidoethyl aniline as the developing substance obtained was a negative purple picture.
  • R is H, Cl, SO l-i, phenylazo

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00175703A 1970-08-29 1971-08-27 Diffusion-resistant purple color couplers for the preparation of photographic color pictures Expired - Lifetime US3808007A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702042922 DE2042922A1 (de) 1970-08-29 1970-08-29 Diffusionsfeste Purpurkomponenten zur Herstellung photographischer Farbbilder

Publications (1)

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US3808007A true US3808007A (en) 1974-04-30

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US (1) US3808007A (OSRAM)
BE (1) BE770974A (OSRAM)
DE (1) DE2042922A1 (OSRAM)
FR (1) FR2107078A5 (OSRAM)
GB (1) GB1325830A (OSRAM)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928044A (en) * 1972-11-15 1975-12-23 Fuji Photo Film Co Ltd Magenta coupler-containing photographic silver halide materials
US3935015A (en) * 1973-02-22 1976-01-27 Fuji Photo Film Co., Ltd. Silver halide color photographic materials containing 3-anilino-5-pyrazolane couplers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD103976A1 (OSRAM) * 1972-07-04 1974-02-12

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983608A (en) * 1958-10-06 1961-05-09 Eastman Kodak Co Yellow-colored magenta-forming couplers
US3127269A (en) * 1961-09-11 1964-03-31 Colour photography
GB1035959A (en) * 1963-11-13 1966-07-13 Ilford Ltd Sulphonated pyrazolone derivatives and their use in colour photography
US3677764A (en) * 1968-08-14 1972-07-18 Agfa Gevaert Ag Silver halide emulsion containing purple coupler for color photography and process of making the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983608A (en) * 1958-10-06 1961-05-09 Eastman Kodak Co Yellow-colored magenta-forming couplers
US3127269A (en) * 1961-09-11 1964-03-31 Colour photography
GB1035959A (en) * 1963-11-13 1966-07-13 Ilford Ltd Sulphonated pyrazolone derivatives and their use in colour photography
US3677764A (en) * 1968-08-14 1972-07-18 Agfa Gevaert Ag Silver halide emulsion containing purple coupler for color photography and process of making the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928044A (en) * 1972-11-15 1975-12-23 Fuji Photo Film Co Ltd Magenta coupler-containing photographic silver halide materials
US3935015A (en) * 1973-02-22 1976-01-27 Fuji Photo Film Co., Ltd. Silver halide color photographic materials containing 3-anilino-5-pyrazolane couplers

Also Published As

Publication number Publication date
FR2107078A5 (OSRAM) 1972-05-05
DE2042922A1 (de) 1972-03-02
BE770974A (nl) 1972-02-07
GB1325830A (en) 1973-08-08

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