US3369899A - Photographic materials containing aroylacetanilide type color couplers - Google Patents

Photographic materials containing aroylacetanilide type color couplers Download PDF

Info

Publication number
US3369899A
US3369899A US381230A US38123064A US3369899A US 3369899 A US3369899 A US 3369899A US 381230 A US381230 A US 381230A US 38123064 A US38123064 A US 38123064A US 3369899 A US3369899 A US 3369899A
Authority
US
United States
Prior art keywords
group
color
aroylacetanilide
silver halide
halide emulsion
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
US381230A
Other languages
English (en)
Inventor
Cat Arthur Henri De
Verbrugghe Marcel Hendrik
Roosen Raymond Albert
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.)
Gevaert Photo Producten NV
Original Assignee
Gevaert Photo Producten NV
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 Gevaert Photo Producten NV filed Critical Gevaert Photo Producten NV
Application granted granted Critical
Publication of US3369899A publication Critical patent/US3369899A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/59—Nitrogen analogues of carboxyl groups
    • 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
    • G03C7/362—Benzoyl-acetanilide couplers

Definitions

  • a photographic light-sensitive color material comprising a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wheren on color development, by use of approprate color couplers, a cyan, a magenta, and a yellow image is respectively formed.
  • color couplers should meet various requirements according to the way wherein the color material is prepared and the purpose for which it is used.
  • the color couplers for the different color separation images have to be incorporated into the hydrophilic silver halide emulsion layers in non-migratory form.
  • This can be achieved e.g. by using a color coupler which is sufiiciently watersoluble and which is provided with a sufiiciently large organic radical for inhibiting migration of the color coupler into the hydrophilic silver halide emulsion layer or by using a lipophilic color coupler which, dissolved in an organic solvent, is dispersed into the silver halide emulsion layer.
  • color couplers which on color development form dyestuffs which are resistant to the action of light, humidity and heat.
  • a class of color couplers for yellow of the known ketomethylene type, more especially of the aroyl acetarylide type has now been found, which color couplers on color development with an aromatic primary amine developing substance form dyestuffs which possess besides a very good stability against light an exceptionally good stability against humidity and heat.
  • ketomethylene color couplers of the aroyl acetarylide type are characterized by the presence of at least one sulphonic acid group in the aroyl part of the molecule, by an arylide part which may be further substituted by one or more substituents which have not a watersolubilizing character, and by the presence of a group inhibiting migration either in the aroyl part or in the arylide part of the molecule.
  • the sulphonic acid group(s) may be bound directly to the aromatic nucleus of the aroyl group or may be present on an aromatic nucleus which is linked to the aromatic nucleus of the aroyl group by means of a bivalent radical.
  • color couplers for yellow according to the invention wherein at least one sulphonic acid group is directly bound to the aromatic nucleus of the aroyl group correspond to the following general formula:
  • R1 Ra wherein R represents a sulphonic acid group or salt form thereof
  • R represents a hydrogen atom, a substituent having either a water-solubilizing character or not such as a halogen atom, an alkoxy group and a sulphonic acid group or salt formthereof, or a group inhibiting migration such as a n-hexadecyloxy group,
  • R represents a hydrogen atoms, a substituent having no water-solubilizing character, for instance a group inhibiting migration for instance the group -XR, wherein X represents a chemical bond, an oxygen atom, a sulphur atom, a sulphonyl group, a SO NH group, a ,NHSO group, a CONH group or a NHCO group, and R represents an acyclic aliphatic hydrocarbon radical containing from 5 to- 20 carbon atoms, and
  • R represents a hydrogen atom, a substituent having no water-solubilizing character such as an alkoxy group, a halogen atom, an alkyl sulphonyl group or a substituted alkyl sulphonyl group such as a -SO CHF group, or the atoms necessary to form a fused aromatic system which may be'further substituted such as an aromatic system of the naphthalene series, at .least one of R and R being a group inhibiting migration.
  • a substituent having no water-solubilizing character such as an alkoxy group, a halogen atom, an alkyl sulphonyl group or a substituted alkyl sulphonyl group such as a -SO CHF group, or the atoms necessary to form a fused aromatic system which may be'further substituted such as an aromatic system of the naphthalene series, at .least one of R and R being a group inhibiting migration.
  • Y-RI1 wherein R R and R have the same significance 'as set forth Y represents a bivalent radical such as a -CONH group, a 4O NH-- group and a -NH-CONH- group.
  • the copper salt is soluble in chlorof0rm ).
  • the reaction mixture is acidified with hydrogen chloride.
  • the a-fiuorosulphonylbenzoylaacetyl-acetic acid ethyl ester is set free.
  • the chloroform layer is separated, washed with water until acid-free and evaporated till an oily residue remains.
  • This residue is converted for purification purposes into the copper salt by means of a solution of copper (II) acetate in alcohol, and after separation of-the green precipitate formed set free again with acid.
  • the fi-dicarbonyl compound is obtained either as an oil which is distilled off or as a solid product which is treated with hexane.
  • reaction mixture is heated till reflux temperature 50 and a mixture of xylene and ethanol formed during the Specific examples of color couplers for yellow according to the present invention wherein a .sulphonic acid group in the aroyl part of the molecule is bound to an aromatic nucleus which is linked to the aromatic nucleus of the aroyl part by means of a bivalent radical, are:
  • Z represents a -COCl radical, a SO Cl radical or a -NCO radical
  • W a CO- radical, a SO radical or a -NHCO radical.
  • the nitro product obtained is reduced in the presence of Raney nickel as catalyst in a dioxan solution under a pressure of 105 kg./sq. cm. of hydrogen at 70 C. Once the calculated amount of hydrogen has been used up the catalyst is filtered oil. In the filtrate a precipitate is formed which is filtered off and recrystallized from benzene.
  • the a (3' aminobenzoyl) 2-n-hexadecyloXy-acetanilide (b') is obtained in the form of white crystals. Melting point: 112 C.
  • Hydrogen chloride is gradually set free and the initially formed precipitate of amine hydrochloride dissolves slowly. After the said reflux period a clear light yellow solution is obtained wherein on cooling till room temperature a white granular product precipitates which is separated and recrystallized from acetonitrile, Melting point: 104 C.
  • sulphofluoride derivative is hydrolyzed therefor in an aqueous solution of 3 mole of sodium hydroxide and the resulting clear solution, after adjusting the pH to agree with the pH of the emulsion applied, is added to the silver halide emulsion in the form of a 5 to aqueous solution.
  • the non-migratory color couplers for yellow are mixed homogeneously in dissolved state with the lightsensitive silver halide emulsion, preferably immediately before the coating of the emulsion. They may also be added to the composition of a water-permeable nonlight-sensitive layer, which is in direct contact with the light-sensitive silver halide emulsion layer or they may be incorporated into a non-light-sensitive layer, which is separated from the light-sensitive layer by a waterpermeable non-light-sensitive layer.
  • the silver halide emulsion contains'the usual colloids such as gelatin, poly- (vinyl alcohol), collodion or other suitable natural or synthetic colloids.
  • the photographic emulsion may further contain usual ingredients such as hardeners, chemical sensitizing agents, optical sensitizing agents, plasticizers, development accelerators, stabilizing agents and wetting agents.
  • the color couplers for yellow are added usually to a bluesensitive silver halide emulsion. According to the most conventionally applied procedure this silver halide emulsion is coated as the last color coupler-containing layer of a photographic multilayer color material.
  • a photographic multilayer color material usually consists in the given sequence of a support, a red-sensitized siver halide emulsion layer with a color coupler for cyan, a greensensitized silver halide emulsion layer with a color coupler for magenta and a blue-sensitive silver halide emulsion layer with a color coupler for yellow.
  • the support of this multilayer material may consist of paper, glass, cellulose nitrate, a celluose ester such as cellulose triacetate, polyester, polystyrene or another synthetic or natural resin.
  • a yellow filter layer is generally present which comprises usually colloidal silver dispersed in gelatin.
  • the sulphofiuoride derivatives may be applied as color couplers for yellow according to the present invention in the so-called droplet emulsions. .(cf.. U.S..Patent 2,304,940). 7
  • an exposed silver halide emulsion layer is developed with an aromatic primary amino dveloping substance in the presence of a color coupler for yellow according to the present invention.
  • the color couplers for yellow according to the present invention form on color development with aromatic primary amines such as N-diethyl-p-phenylenediamine yellow dyes which excel by their favorable light absorption in the blue region of the spectrum and little absorption in the other regions. Further, the dyes formed on color development show good resistance to heat, humidity and light which is proved by comparative tests, the description and results of which are given hereinafter.
  • the resistance to humidity and heat of the dyes to be examined is determined from the decrease in density Maximum density Maximum density Percentage Formula of the color coupler at the beginning after storing for I decrease in oi the test 10 days at 0. maximum and 87% RH.
  • the resistance to light of the dyestuffs formed on development with N-diethyl-p-phenylenediamine and which are to be examined is determined from the decrease in density of a developed wedge print on exposing it for a certain time (e.g., 16 h.) to light of a Xenon Arc Fadeometer (daylight spectrum).
  • the following table gives a clear idea about the resistcoupler for yellow of the aroylacetanilide type wherein the aroyl part of the aroylacetanilide molecule comprises at least one sulfonic acid group, the anilide part of the aroylacetanilide molecule contains only substituents selected from the group consisting of hydrogen and a hydrophobic group, and the aroylacetanilide molecule contains a group for inhibiting migration in a member of the group consisting of the aroyl part and anilide part of the molecule.
  • Photographic multilayer color material comprising, in non-migratory state, in a member selected from the group consisting of a light-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent to a silver halide emulsion layer a color coupler for yellow corresponding to the following general formula:
  • the acid form as well as the salt form of this group or substituent are intended, the salt form carrying preferably as cation an alkali metal cation, an ammonium group or an amine salt group.
  • a photographic material comprising a silver halide emulsion layer and a color coupler for yellow of the .aroylacetanilide type wherein aroyl part or the aroyl- :acetanilide molecule comprises at least one sulfonic acid group, the anilide part of the aroylacetanilide molecule contains only substituents selected from the group consisting of hydrogen and a hydrophobic group, and the aroylacetanilide molecule contains a group for inhibiting migration in a member of the group consisting of the aroyl part and anilide part of the molecule;
  • Photographic multilayer color material comprising, in non-migratory state, in a member selected from the group consisting of a light-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent to a silver halide emulsion layer a color Z is a sulfonated benzoyl group;
  • R represents a member selected from the group consisting of a hydrogen atom and a hydrophobic group
  • R represents a member selected from the group consisting of a hydrogen atom, a hydrophobic group and the atoms necessary to form a fused aromatic nucleus, said color coupler having at least one group for inhibiting migration.
  • Photographic multilayer color material comprising, in non-migratory state, in a member selected from the group consisting of a light-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent to a silver halide emulsion layer a color coupler for yellow corresponding to the following general formula:
  • Y represents a bivalent radical selected from the group consisting of CONH, SO NH, and
  • R' represents a sulfonated aromatic nucleus
  • R represents a member selected from the group consisting of a hydrogen atom, a hydrophilic group and a hydrophobic group
  • R represents a member selected from the group consisting of a hydrogen atom, and a hydrophobic group
  • R represents a member selected from the group consisting of a hydrogen atom, a hydrophobic group and the atoms necessary to form a fused aromatic nucleus, at least one of R and R being a group inhibiting migration.
  • Photographic multilayer color material comprising three silver halide emulsion layers which are differently optically sensitized wherein a member selected from the group consisting of the blue-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent thereto incorporates, in non-migratory state, a color coupler for yellow of the aroylacetanilide type wherein the aroyl part of the aroylacetanilide molecule comprises at least one sulfonic acid group, the anilide part of the aroylacetanilide molecule contains only substituents selected from the group consisting of hydrogen and a hydrophobic group, and the aroylacetanilide molecule contains a group for inhibiting migration in a member of the group consisting of the aroyl part and anilide part of the molecule.
  • Photographic multilayer color material comprising three silver halide emulsion layers which are differently optically sensitized wherein a member selected from the group consisting of the blue-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent thereto incorporates, in non-migratory stateTa color coupler for yellow corresponding to the following general formula:
  • Z is a sulfonated benzoyl group
  • R represents a member selected from the group consisting of a hydrogen atom and a hydrophobic group
  • R represents a member selected from the group consisting of a hydrogen atom, a hydrophobic group and 18 the atoms necessary to form a fused aromatic nucleus, said color coupler having at least one group for inhibiting migration.
  • Photographic multilayer color material comprising three silver halide emulsion layers which are differently optically sensitized wherein a member selected from the group consisting of the blue-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent thereto incorporates, in non-migratory state, a color coupler for yellow corresponding to the following general formula:
  • Y represents a bivalent radical selected from the group consisting of CONH--, SO NH, and
  • R represents a sulfonated aromatic nucleus
  • R represents a member selected from the group consisting of a hydrogen atom, a hydrophilic group and a hydrophobic group
  • R represents a member selected from the group consisting of a hydrogen atom, and a hydrophobic group
  • R represents a member selected from the group consisting of a hydrogen atom, a hydrophobic group and the atoms necessary to form a fused aromatic nucleus, at least one of R and R being a group inhibiting migration.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US381230A 1963-07-09 1964-07-08 Photographic materials containing aroylacetanilide type color couplers Expired - Lifetime US3369899A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE42767 1963-07-09

Publications (1)

Publication Number Publication Date
US3369899A true US3369899A (en) 1968-02-20

Family

ID=3840368

Family Applications (1)

Application Number Title Priority Date Filing Date
US381230A Expired - Lifetime US3369899A (en) 1963-07-09 1964-07-08 Photographic materials containing aroylacetanilide type color couplers

Country Status (4)

Country Link
US (1) US3369899A (en))
BE (1) BE634665A (en))
CH (1) CH458065A (en))
GB (1) GB1039965A (en))

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3645742A (en) * 1968-01-05 1972-02-29 Agfa Gevaert Nv Color photography

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2350138A (en) * 1940-08-22 1944-05-30 Eastman Kodak Co Nondiffusing acylacetyl sulphonamide coupler
US2662913A (en) * 1952-07-11 1953-12-15 American Cyanamid Co Diaminofluorene derivatives
US2704709A (en) * 1949-07-16 1955-03-22 Gen Aniline & Film Corp Masking process for multilayer photographic color film
US2836620A (en) * 1954-03-17 1958-05-27 Dow Chemical Co Amino sulfonic acids and salts thereof
US2895825A (en) * 1954-03-18 1959-07-21 Agfa Ag Production of photographic colour images with heterocyclic developers
US2933391A (en) * 1956-09-06 1960-04-19 Eastman Kodak Co Photographic emulsions containing 5-pyrazolone coupler compounds
US2983608A (en) * 1958-10-06 1961-05-09 Eastman Kodak Co Yellow-colored magenta-forming couplers

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2350138A (en) * 1940-08-22 1944-05-30 Eastman Kodak Co Nondiffusing acylacetyl sulphonamide coupler
US2704709A (en) * 1949-07-16 1955-03-22 Gen Aniline & Film Corp Masking process for multilayer photographic color film
US2662913A (en) * 1952-07-11 1953-12-15 American Cyanamid Co Diaminofluorene derivatives
US2836620A (en) * 1954-03-17 1958-05-27 Dow Chemical Co Amino sulfonic acids and salts thereof
US2895825A (en) * 1954-03-18 1959-07-21 Agfa Ag Production of photographic colour images with heterocyclic developers
US2933391A (en) * 1956-09-06 1960-04-19 Eastman Kodak Co Photographic emulsions containing 5-pyrazolone coupler compounds
US2983608A (en) * 1958-10-06 1961-05-09 Eastman Kodak Co Yellow-colored magenta-forming couplers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3645742A (en) * 1968-01-05 1972-02-29 Agfa Gevaert Nv Color photography

Also Published As

Publication number Publication date
CH458065A (fr) 1968-06-15
GB1039965A (en) 1966-08-24
BE634665A (en))

Similar Documents

Publication Publication Date Title
JPH0549975B2 (en))
US2998314A (en) Color photography
US3002836A (en) Cyan color former for color photography
US3615505A (en) Silver halide emulsion containing 2-pyrazolin-5-one color coupler
US3563745A (en) Silver halide photographic materials containing 1-arylmethyl-2-pyrazolin-5-one color couplers
US3013879A (en) Production of color photographic images
US4230851A (en) Process for the production of 2-equivalent yellow couplers
US3245787A (en) Production of color photographic images
US3222176A (en) Photographic colour images from amino substituted phenols
US4342825A (en) Photographic elements containing cyan-forming color couplers
US3369899A (en) Photographic materials containing aroylacetanilide type color couplers
US2673801A (en) Production of color photographic images
US3623871A (en) Photographic color process utilizing 2-pyrazolin-5-one couplers
US3337344A (en) Color photographic silver halide emulsion
US3056674A (en) Color formers for producing yellow dye images by color development
US3393040A (en) Silver halide photographic elements containing sulfonic acid substituted aroylacetarylide couplers
US3892576A (en) Photographic water-insoluble compounds having a hydrophobic diffusion-fast substituent
US3930861A (en) Silver halide emulsions containing 3-anilino-2-pyrazolin-5-one color couplers
EP0037597B1 (en) Novel cyan-forming couplers and photographic elements containing such couplers
US2728658A (en) Benzoyl acetanilide couplers for color photography
US3462270A (en) Color photography utilizing 1-fluoroalkyl - 2 - pyrazoline - 5 - one colour couplers
US3249431A (en) Production of color photographic images
US3503748A (en) Light-sensitive photographic silver halide layer for the color developing process
US3652286A (en) Color photographic silver halide multi-layer material containing cyan-forming couplers
US3843366A (en) Yellow forming colour couplers for photographic silver halide material