US3212894A - Non-diffusing magenta color couplers - Google Patents

Non-diffusing magenta color couplers Download PDF

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Publication number
US3212894A
US3212894A US160667A US16066761A US3212894A US 3212894 A US3212894 A US 3212894A US 160667 A US160667 A US 160667A US 16066761 A US16066761 A US 16066761A US 3212894 A US3212894 A US 3212894A
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United States
Prior art keywords
color
ethyl
coupler
couplers
formula
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Expired - Lifetime
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US160667A
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English (en)
Inventor
Menzel Karl-Heinz
Ulrich Hans
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Agfa Gevaert NV
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Agfa AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C07D231/26—1-Phenyl-3-methyl-5- pyrazolones, unsubstituted or substituted on the phenyl ring
    • 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 present invention relates to color couplers in which the non-diffusing group comprises a long aliphatic chain substituted by two hydroxy groups, the silver halide emulsions containing such couplers and to the production of colored photographic images in the presence of such couplers.
  • magenta couplers containing a 9,10-dihydroxyheptadecyl substituent radical serve as very useful color couplers for color photographic materials.
  • This advantageous and unexpected efiect of the dihydroxyheptadecyl radical is not restricted to only certain special color coupler structures but can be observed with various magenta couplers.
  • the color coupler structure of the color couplers is selected only according to the requirement of the color photographic material in which the coupler containing the dihydroxyheptadecyl radical is to be used. Especially suitable are, however, color couplers of the pyrazolone or pyrazolinobenzimidazole series.
  • Color couplers carrying such a dihydroxyheptadecyl substituent do not show any tendency to crystallize in the photographic layer, and a solution of the color former in gelatin remains completely clear for a long time at 40 C.; a flattening of the gradation compared with a freshly prepared solution is not observed.
  • Couplers of the pyrazolone and pyrazolinobenzimidazole series containing a dihydroxyheptadecyl radical can be prepared'in conventional manner by using the ethyl ester of 9,10-dihydroxystearoylacetic acid instead of ethyl stearoylacetate as starting material for the pyrazolone.
  • 1.5 g. of this color coupler is suspended in 5 cc. of methanol, dissolved by addition of 5 cc. of l-normalsodium hydroxide solution and cc. of water and made up with water to 100 cc.
  • the solution is added to 100 cc. of a silver halide emulsion, which is cast in known manner on a support.
  • magenta image After exposure and development with diethylamino aniline, a magenta image is obtained with an absorption maximum at 530 millimicrons.
  • the color component solution of the magenta coupler VI in which the hydroxy groups are lacking, and which is used for comparison purposes, becomes cloudy with return of the pH-value to 7.
  • EXAMPLE 2 14 g. of 4-phenoxy-3-sulphophenyl hydrazine, 6 g. of anhydrous sodium acetate, 40 cc. of water, 7 cc. of glacial acetic acid, 22 g. of ethyl 9,10-dihydroxystearoylacetate and 40 cc. of n-propanol are refluxed for 2 hours. Thereafter, the mixture is acidified with 20% hydrochloric acid and the liquid is decanted off from the semi-solid mass. The product is triturated with ethyl acetate, suction-filtered and thereafter extracted with acetone. There are obtained about g. of 1-(4'-phenoxy-3'-sulphophenyl)- 3-(9, 10-dihydroxyheptadecyl)-5 -pyrazol0ne (Formula II).
  • EXAMPLE 3 12 g. of 4-ethoxyphenyl hydrazine-3-sulphonic acid, 6 g. of sodium acetate, 40 cc. of water, 7 cc. of glacial acetic acid, 22 g. of ethyl 9,10-dihydroxystearoylacetate and 40 cc. of n-pr-opanol are boiled under reflux for 2 hours. The mixture is then acidified with hydrochloric acid, cooled with ice and suction-filtered. The residue is extracted with acetone and there are obtained about 15 g. of 1-(4'-ethoxy-3'-sulphophenyl)-3(9,10-dihydroxyheptadecyl)-5-pyrazolone (Formula III).
  • EXAMPLE 4 13.5 g. of 2-hydrazinobenzthiazole-S-sulpl1onic acid, 50 cc. of water, 5 g. of anhydrous sodium acetate, 12.5 cc. of glacial acetic acid, '25 g. of ethyl 9,10-dihydroxystearoylacetate and 30 cc. of isopropanol are stirred for 3 hours at 65 C. Precipitation is carried out with concentrated hydrochloric acid and ice, the mixture is suction-filtered and the residue extracted with acetone. About 16 g. of the color coupler represented by Formula IV is obtained. The processing of 1.5 g. of this color coupler in a manner similar to that described in Example 1 supplies a magenta image with an absorption maximum at 550 millimicrons.
  • EXAMPLE 5 12 g. of 2-nitrophenylhydrazine-4-sulphonic acid, 6 g. of anhydrous sodium acetate, 50 cc. of water, 10 cc. of glacial acetic acid,'22 g. of ethyl 9,10-dihydroxystearoylacetate and cc. of isopropanol are stirred for minutes at 80 C., 30 cc. of 45% sodium hydroxide solution are thereafter introduced dropwise and the solution is boiled for 2 hours under reflux. After acidification with 20% hydrochloric acid, the mixture is extracted with ethyl acetate and separated from the aqueous phase in a separating funnel. The ester extract is washed neutral, dried with sodium sulphate and concentrated in vacuo. The remaining oil is dissolved in 200 cc. of methanol and about 5 cc. of concentrated sodium hydroxide solution (pH 10).
  • magenta coupler represented by Formula V.
  • a color photographic negative film is built up in the usual manner upon an acetyl cellulose support casting thereon a silver bromide emulsionwith a diffusion-re sistant cyan coupler (for instance, the sodium salt of 1 hydroxy 2 naphthoic acid 2 N methyl N- octadecy1-5-sulphonic acid anilide), this being followed by a silver bromide emulsion with the compound described in Example 5 as magenta component, after which a yellow filter layer is cast and on top of the latter a silver bromide emulsion layer with a yellow coupler (for instance, the sodium salt of 4-stearoylaminobenzoyl-acet- 3-5'-dicarboxyanilide).
  • the matching of the three emulsion layers is effected in conventional manner in such a way that after exposure of a stepped wedge with white light, the color development leads to a neutral grey neg.- tive stepped wedge.
  • the negative film is exposed to an object to be reproduced processed in ordinary processing baths including a developer solution containing a p-diethylamino aniline developer substance to produce a multi-color negative image, and thereafter printed onto a multi-color positive material, wherein after ordinary processing a positive image of very good color quality is obtained.
  • magenta coupler of the above described color-photographic material is replaced with one of the following color couplers:
  • the light-sensitive emulsions containing one of the above listed color couplers are prepared as described in Example 8.
  • EXAMPLE 7 The color coupler of Formula XVI, which is 8-carboxy 3 dihydroxy heptadecyl 1,5 pyrazolinobenzirnidaZ-ole (1,2), .is prepared by reaction of 2-nitrophenyl-hydrozine-4-carboxylic acid with ethyl 9,10-dihydroxystearoylacetate, hydrogenation of nitrophenyl pyrazolone obtained thereby and cyclization as described in Example 1.
  • 1.5 -g. of this color coupler are suspended in 5 cc. of methanol, dissolved by addition of 5 cc. of l-normalsodium hydroxide solution and cc. of water and made up with water to 100 cc.
  • the solution is added to 100 cc. of a silver halide emulsion, which is cast in known manner on a support.
  • magenta image After exposure and development with diethylamino aniline, a magenta image is obtained with an absorption maximum at 535 millimicrons.
  • EXAMPLE 8 The color coupler of Formula VII is prepared by reaction of 3-chlorophenyl hydrazine with ethyl 9,10-dihydroxystearoylaoetate.
  • the color couplers can be used in any color photographic material such as mono-layer or multilayer positive or negative material or reversal color films.
  • the non-ditfusing color couplers according to the invention can be used in combination with any sensitizers, antifog agents, stabilizers or the like which are known to be employed in color photographic material.
  • the layer arrangement or sensitizationcolor-relationship are not especially critical.
  • the binding agent of the layers in which the color couplers are to be used is preferably gelatin
  • other layer forming hydrophilic agents can be used such as carboxy cellulose, polyvinyl alcohol or the like.
  • the processing of the exposed color material, containing in one layer a magenta coupler according to the invention, is accomplished in a manner well known by first developing the material with a developer composition containing a color forming developer.
  • Said developers generally spoken are characterized by a primary amino group or a substituted amino group, the su'bstituent of which is split off during the development, e.g., as described in German Patent No. 926,713.
  • Very useful color developers are, for example, N,N diethyl p phenylene diamine, N ethyl- N hydroxy ethyl p phenylene diamine, N butyl- N sulphobutyl p phenylene diamine, N ethyl N- methyl sulfoamino-ethyl-p-phenylene-diamine or derivatives thereof being substituted in the phenylene nucleus, furthermore, 4-aminopyrazolone and derivatives thereof.
  • the developer composition may be alkalized -by alkalimetal carbonates, tertiary alkali-metal phosphates or the like alone or in combination with small amounts of alkalimetal hydroxides.
  • the developers may contain any stabilizing agents, antifog agents and compounds protecting the composition against oxidation such as alkali sulphites or salts of hydroxylamine.
  • the developing is followed by bleaching and fixing the color films.
  • a process for the production of a magenta-colored photographic image which comprises developing an exposed silver halide emulsion layer containing a non-diffusing color coupler that is capable of forming a magentacolored image upon reaction with the oxidation products of a primary amine color-forming developer, which color coupler is a member of the group consisting of 5-pyrazolone and 1,S-pyrazolinobenzimidazole(l',2') color couplers substituted in the 3 position by a 9,10-dihydroxyheptadecyl radical, and subsequently bleaching and fixing the said developed silver halide emulsion layer.
  • a photographic material composed of a plurality of superimposed silver halide layers each of which is sensitive to dilferent regions of the visible light spectrum, at least one layer of which contains a color coupler of the group consisting of 5-pyrazolone and 1,5-pyrazolinobenzimidazole(1,2) color couplers substituted in the 3 position by a 9,10-dihydroxyheptadecyl radical.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
US160667A 1960-12-24 1961-12-19 Non-diffusing magenta color couplers Expired - Lifetime US3212894A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA36369A DE1127220B (de) 1960-12-24 1960-12-24 Verfahren zur Herstellung farbiger photographischer Bilder nach dem Farbentwicklungsverfahren

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US (1) US3212894A (fr)
BE (1) BE611885A (fr)
DE (1) DE1127220B (fr)
GB (1) GB939904A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032345A (en) * 1974-08-02 1977-06-28 Fuji Photo Film Co., Ltd. Silver halide materials containing photographic color couplers with isothiocyanato groups
US4032346A (en) * 1974-08-01 1977-06-28 Fuji Photo Film Co., Ltd. Silver halide emulsion containing two-equivalent magenta coupler
US4040836A (en) * 1974-07-18 1977-08-09 Fuji Photo Film Co., Ltd. Silver halide emulsion containing two-equivalent coupler
US20060048673A1 (en) * 2004-09-07 2006-03-09 Eastman Kodak Company Solubilized dyes for inks

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69523429T2 (de) * 1994-12-30 2002-06-27 Eastman Kodak Co., Rochester Photographisches Element das einen Pyrazolon-Pug-freisetzenden Kuppler enthält und Bildverfahren das dieses verwendet
US5576167A (en) * 1994-12-30 1996-11-19 Eastman Kodak Company Photographic element containing a stable aryloxypyrazolone coupler and process employing same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2213986A (en) * 1938-04-08 1940-09-10 Ilford Ltd Production of colored photographic images
US2892714A (en) * 1954-07-08 1959-06-30 Agfa Ag Photographic color development with pyrazoline developers
US3061432A (en) * 1958-06-21 1962-10-30 Agfa Ag Pyrazolino benzimidazole color coupler

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2213986A (en) * 1938-04-08 1940-09-10 Ilford Ltd Production of colored photographic images
US2892714A (en) * 1954-07-08 1959-06-30 Agfa Ag Photographic color development with pyrazoline developers
US3061432A (en) * 1958-06-21 1962-10-30 Agfa Ag Pyrazolino benzimidazole color coupler

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040836A (en) * 1974-07-18 1977-08-09 Fuji Photo Film Co., Ltd. Silver halide emulsion containing two-equivalent coupler
US4032346A (en) * 1974-08-01 1977-06-28 Fuji Photo Film Co., Ltd. Silver halide emulsion containing two-equivalent magenta coupler
US4032345A (en) * 1974-08-02 1977-06-28 Fuji Photo Film Co., Ltd. Silver halide materials containing photographic color couplers with isothiocyanato groups
US20060048673A1 (en) * 2004-09-07 2006-03-09 Eastman Kodak Company Solubilized dyes for inks

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Publication number Publication date
DE1127220B (de) 1962-04-05
GB939904A (en) 1963-10-16
BE611885A (fr)

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