US3574626A - Photographic silver halide emulsions containing 1-carbomylmethyl-pyrazolone couplers - Google Patents

Photographic silver halide emulsions containing 1-carbomylmethyl-pyrazolone couplers Download PDF

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Publication number
US3574626A
US3574626A US801786A US3574626DA US3574626A US 3574626 A US3574626 A US 3574626A US 801786 A US801786 A US 801786A US 3574626D A US3574626D A US 3574626DA US 3574626 A US3574626 A US 3574626A
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United States
Prior art keywords
silver halide
color
carbomylmethyl
solution
couplers
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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
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US801786A
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English (en)
Inventor
Friedrich-Wilhelm Kunitz
Willibald Pelz
Fritz Nittel
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • 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
    • 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
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • 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

  • This invention relates to a color photographic material which has at least one silver halide emulsion layer which contains a magenta-forming coupler.
  • color couplers is understood to mean compounds which will react with the oxidation products of color photographic developers, especially those of the phenylene diamine type, to form colored compounds.
  • Such couplers must satisfy many requirements; for eX- ample they should couple as rapidly as possible with the oxidised color developer to form the dye.
  • the resulting dye should, as far as possible, only adsorb in the required region of the spectrum whereas any side absorptions in other regions of the spectrum are undesirable.
  • the dyes produced should be as light-fast as possible and be stable even under extreme conditions of high temperature and atmospheric moisture such as occur in the tropics. Adequate resistance to tropical conditions is, of course, also necessary for the color couplers which are incorporated in the light-sensitive layer.
  • the previously known magenta-forming couplers have been particularly unsatisfactory in this last respect. Also, the known magenta-forming couplers do not produce dyes on color development of the required brilliance.
  • magenta-forming couplers which not only have these required properties but also show satisfactory stability under tropical conditions and have high brilliance and good fastness to light.
  • magenta-forming couplers for photographic silver halide emulsion layers are l-carbomylmethyl-pyrazolone compounds of the following formula:
  • R is (1) alkyl preferably with up to 20 carbon atoms, (2) an aryla-mino group, preferably a phenylamino group, in which the phenyl group may be further substituted, e.g. with halogen, such as chlorine or bromine, alkyl, alkoxy, sulfo or carboxyl, or (3) an acylamino group in which the acyl groups may be derived from long chain aliphatic carboxylic acids or from benzene carboxylic acids which may carry further substituents such as halogen, alkyl, alkoxy, phenoxy, sulfo or carboxyl; the acyl groups can 3,574,626 Patented Apr. 13, 1971 2 t to, N 3 i I 00 N sonar Amara-@411
  • the compounds according to the invention are prepared by methods known per se. The method of preparation of coupler 2 is described in detail below. The other compounds are prepared in a similar way.
  • the reaction mixture was then poured into a mixture of 300 ml. of 5 N HCl and ice and then made acid to Congo red with 5 N HCl.
  • the waxy product was separated by suction filtration and washed with water.
  • the crude product was stirred up with a little methanol, separated by suction filtration and washed with methanol.
  • the crude product was purified by recrystallization from 250 ml. of alcohol with the addition of active charcoal. The yield of yellowish crystals was 50 g., the melting point 103-l05 C.
  • the color couplers according to the invention have excellent stability to moist heat.
  • the dyes produced from them in the course of the color-producing development are also stable under extreme climatic conditions at elevated temperatures and in very humid conditions. In addition, they have excellent fastness to light. Their absorption properties are very good.
  • the color couplers according to invention couple extremely rapidly with the usual developers.
  • the dyes obtained on color development with the color couplers according to the invention have an excep tionally high brilliance.
  • the color couplers according to the invention may be incorporated in a difiiusion-fast form into the light-sensitive silver halide layers. This can be achieved in known manner by dissolving color couplers substituted with long chain alkyl radicals and with water-solubilising groups in the casting solution so that they are present in the emulsion layer in dissolved form. Alternatively the color couplers may be emulsified in the emulsion layer. Such proc esses have been known for a long time and can be easily applied in the present case.
  • aqueous solutions of the new compounds may be mixed with the silver halid emulsions.
  • the new compounds as long as they are hydrophobic, are emulsified in gelatin, using a solvent, with or without an oil-forming agent, the emulsion is dried, again swelled in water, and mixed with the silver halide emulsion.
  • the new dye-forming substances may be added not only to the light sensitive silver halide emulsion layer itself but also to an adjacent non-sensitive layer. They may also be developed-in into the photographic material together with the color developer.
  • Any color-producing developers which contain a primary amino group may be used for the development.
  • Those of the p-phenylenediamine type e.g. N.N-diethyl-pphenylenediamine, N monomethyl p-phenylenedia-mine, N,N-dimethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, N butyl N w-sulfobutyl-p-phenylenediamine and the like are preferred.
  • hydrophilic film forming agents such as protein, especially gelatin, polyvinyl alcohol, polyvinyl-pyrrolidine, cellulose derivatives such as carboxyalkyl-cellulose, especially carboxymethyl cellulose, derivatives of alginic acid and their alkali metal salts or esters are suitable for use as binders for the layers.
  • magenta-forming couplers according to the invention are preferably added to green-sensitized photographic emulsions.
  • Such emulsions may in the usual way contain in addition chemical sensitizers.
  • these layers may be stabilized by known additives, especially by the azaindene dervatives described in the discourse by Birr in Z. wiss. Photo. 47 (1952), pages 2-28.
  • Example-5 milli-moles of coupler 2 are dissolved in 125 ml. of an aqueous sodium hydroxide solution of approximate pH 9.
  • 62.5 g. of a silver bromide emulsion which contains 80 g. of silver bromide and 82.5 of gelatin per kilogram are mixed with 187.5 g. of a 7.5% aqueous gelatin solution and the above color coupler.
  • the mixture has a pH of about 6.5. 100 ml. of a 1% methanolic solution of 4- hydroxy-6-methyl-l,3,3a,7-tetraazainden, 120 ml. of a 5% aqueous saponin solution and 60 ml. of a 0.5% aqueous solution of chromoacetate are added.
  • the mixture is then made up to 900 ml. with water.
  • the casting solution is cast on a cellulose acetate support and dried.
  • the film is developed in a conventional sensitometer behind a grey step wedge, using a conventional color-forming developer which contains N-ethyl-N-w-sulfobutyl-pphenylene diamine as developer. It is treated with a bleaching bath and fixed in known manner. A magenta step wedge with brilliant colors is obtained.
  • a light-sensitive photographic silver halide emulsion layer which contains a magenta-forming color coupler of the following formula:
  • R is alkyl having up to 20 carbon atoms, an arylamino group or an acylamino group
  • R is hydrogen or alkyl having up to 18 carbon atoms
  • R is hydrogen, alkyl having up to 20 carbon atoms, an
  • R represents an acylamino group in which the acyl group is derived from an aliphatic carboxylic acid which bears a sulfo group or is derived from a benzoic acid which bears a sulfo group.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US801786A 1968-03-05 1969-02-24 Photographic silver halide emulsions containing 1-carbomylmethyl-pyrazolone couplers Expired - Lifetime US3574626A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEA0058350 1968-03-05
DE19681622922 DE1622922A1 (de) 1968-03-05 1968-03-05 Farbkupplerhaltiges photographisches Material

Publications (1)

Publication Number Publication Date
US3574626A true US3574626A (en) 1971-04-13

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US801786A Expired - Lifetime US3574626A (en) 1968-03-05 1969-02-24 Photographic silver halide emulsions containing 1-carbomylmethyl-pyrazolone couplers

Country Status (6)

Country Link
US (1) US3574626A (fr)
BE (1) BE729233A (fr)
CH (1) CH505408A (fr)
DE (1) DE1622922A1 (fr)
FR (1) FR2003277A1 (fr)
GB (1) GB1253711A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4741980A (en) * 1985-09-19 1988-05-03 Konishiroku Photo Industry Co., Ltd. Method for increasing color-fastness of organic coloring matter
WO2007034183A3 (fr) * 2005-09-22 2007-06-14 Astrazeneca Ab Procede

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4741980A (en) * 1985-09-19 1988-05-03 Konishiroku Photo Industry Co., Ltd. Method for increasing color-fastness of organic coloring matter
WO2007034183A3 (fr) * 2005-09-22 2007-06-14 Astrazeneca Ab Procede
US20080269500A1 (en) * 2005-09-22 2008-10-30 Astrazeneca Ab Process for the Preparation of 4-Aminopyrazole Derivatives
JP2009508922A (ja) * 2005-09-22 2009-03-05 アストラゼネカ アクチボラグ ４−アミノピラゾール誘導体の製造方法

Also Published As

Publication number Publication date
CH505408A (de) 1971-03-31
FR2003277A1 (fr) 1969-11-07
GB1253711A (en) 1971-11-17
BE729233A (fr) 1969-09-03
DE1622922A1 (de) 1971-02-25

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