US3779763A - Phenol color couplers - Google Patents

Phenol color couplers Download PDF

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Publication number
US3779763A
US3779763A US00223375A US3779763DA US3779763A US 3779763 A US3779763 A US 3779763A US 00223375 A US00223375 A US 00223375A US 3779763D A US3779763D A US 3779763DA US 3779763 A US3779763 A US 3779763A
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group
hydrogen atom
cyan dye
formula
silver halide
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US00223375A
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English (en)
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P Lau
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Eastman Kodak Co
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C07C323/43—Y being a hetero atom
    • C07C323/44—X or Y being nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • 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
    • G03C7/34—Couplers containing phenols
    • G03C7/346—Phenolic couplers

Definitions

  • Coupler compounds employed to produce cyan photographic dyes are generally of the phenolic or anaphtholic type. A majority of such couplers are known and described as four-equivalent couplers, and are characterized in requiring the development of four lightexposed silver halide molecules in order to ultimately produce one molecule of dye. Also widely used are socalled two-equivalent couplers in which a nonchromophoric coupling off group is substituted in coupling position. Couplers of this type are functionally characterized by requiring the development of only two exposed silver halide molecules during development to obtain one molecule of dye. Known two-equivalent couplers and methods for their utilization are disclosed, for instance, in U.S. Pat. Nos. 3,458,315 and 3,227,155 of Loria and Loria et al. respectively.
  • a coupler should also be stable and produce stable photographic dyes having precise spectral absorption characteristics upon reaction with oxidized developer.
  • Couplers also must possess a number of important ancillary characteristics. It is desirable, for instance, to utilize non-diffusible couplers which require only minimal amounts of high-boiling nonremovable coupler solvents and thereby obtain thinner and more durable photographic elements. It is also important that non-diffusible couplers of the above types be capable of precise incorporation into a silver halide emulsion with no adverse effects on emulsion viscosity, adhesion characteristics, or the unity of an emulsion layer during modern high speed multilayer application onto a film backing.
  • Undesirable changes may also be caused by additives such as wetting agents, color components, etc.; such changes are capable of directly affecting the coating characteristics of the photographic emulsion. This fact is indicated, for instance, on page 250 of the text by Zelikman and Levi, entitled Making and Coating Photographic Emulsions; The Focal Press (1964).
  • Including antihalation and gelatin interlayers up to eight or more separate layers may be applied to a film base to obtain a modern color photographic element (ref. Kirk-Othmer, Vol. 5, pages 8l2-845, Encyclopedia of Chemical Technology (1950). For this reason, coupler-induced changes in the physical properties of a coating may well be as important as coupler reactivity with oxidized developer.
  • U.S. Pat. No. 2,322,376 of the Cleary et al relates to a class of phenol compounds having a floating substituent radical of the formula --(CH SR in which R, is defined as an alkyl, an aryl, a cycloalkyl, a cycloaryl or a naphthenyl radical.
  • R is defined as an alkyl, an aryl, a cycloalkyl, a cycloaryl or a naphthenyl radical.
  • the indicated disclosure fails to point out the surprising advantages of an arylthiomethyl group in the No. 5 position or indicate utilization for color photographic purposes.
  • R is a hydrogen atom, an alkyl group inclusive of an alkyl group of 1-22 carbon atoms (e.g. methyl, dodecyl, docosyl), an aryl group such as a phenyl group or a naphthyl group (e.g. phenyl, chlorophenyl, pentafluorophenyl), an acyl group including a radical of the formula in which R,; is an alkyl group of one to 20 carbon atoms, including substituted alkyl group such as aryloxyalkyl group (e.g.
  • alkylamino group of one to 20 carbon atoms e.g, propylamino and octadecylamino
  • an arylamino group inclusive of a phenylamino group or a naphthylamino group e.g. phenylamino or chlorophenylamino
  • a phenyl group, or a naphthyl group e.g.
  • R and R are each a hydrogen atom, a halo group such as chloro, or bromo, an aryl group such as a phenyl group or a naphthyl group exemplified by phenyl, methylphenyl and dichlorophenyl, also each can be an alkyl group or an alkoxy group wherein the alkyl moieties contain one to [5 carbon atoms and preferably one to four carbon atoms; R is an aryl group, including a phenyl group or a naphthyl group, and exemplified by phenyl, a halophenyl group such as a chlorophenyl or dichlorophenyl, a methylphenyl or a chloromethylphenyl R is a hydrogen atom, or a coupling off group including a halo radical, such as chloro or fluoro, a thiocyan
  • R is a hydrogen atom or an alkyl group such as alkyl of one to 20 carbon atoms exemplified by methyl, octyl and eicosyl; and X is defined as the bivalent group of the formulae S,
  • the reaction as described is unique insofar as it involves a one-step process in which the reaction takes place specifically at a position para to the amine substituent group of the phenol reactant rather than para to the OH group. This is true even in the presence of other substituent groups on the phenol ring, even one or more alkoxy groups.
  • o-amino phenol reactants can be obtained, for instance, by nitration, and reduction of the resulting nitrophenols and by preferential methylation when utilizing secondary amine-substituted reactants.
  • Ballasted non-diffusible dye-forming couplers within the present invention can be conveniently incorporated into a photographic element, particularly into a photographic silver halide emulsion layer thereof by initially dissolving the coupler into a high-boiling and/or one or more low-boiling organic solvents. The resulting solution is then dispersed into a gelatin solution with the aid of an emulsifier, and this coupler dispersion set, noodled, washed, and then melted and dispersed into a light-sensitive silver halide gelatin dispersion and coated onto a film support. Suitable solvents and techniques for this purpose are disclosed, for instance, in U.S. Pat. Nos.
  • Corresponding non-ballasted or lightly substituted diffusible coupler compounds can be conveniently incorporated into a developer solution in accordance with art-recognized techniques as summarized, for instance, on lines 50-65 of section XXII of the abovecited Product Licensing lndex.
  • An effective amount for non-diffusible couplers of the above type can range from about 25-200 mg/ft of coated material, a concentration of 30-50 mg/ft being generally satisfactory. Insofar as diffusible type couplers are concerned, a concentration of about 1.5 gm/liter to 1.9 gm/liter of developer solution is found sufficient.
  • photographic elements suitable for use in the present invention comprise:
  • a support layer such as described in section X of Product Licensing Index, Vol. 92, Publication 9232 (December, 1971). Included among the possible support layers are hydrophobic resin layers which have been electron bombarded as described, for instance, in British Patents Nos. 971,058, 1,060,526 and U.S. Pat. Nos. 2,864,755 and 2,864,756 to improve adhesion of hydrophilic colloid layers coated over them. Such resin layers or film may be either self-supporting or may be coated over another support layer. Specific supports having useful hydrophobic surfaces include polyethylene terephthalate films electron-bombarded to have a contact angle less than 45 (U.S.
  • Patent 3,220,842 an electron-bombarded surface comprising a chromium halide
  • U.S. Patent 3,1 17,865 or electron-bombarded hardened gelatin coated papers Belgian Patent No. 671,661
  • An antihalation layer attached to the support layer such as a dye-containing gelatin starch, etc., as described, for instance, in Glafkides Photographic Chemistry," Volume 1, pages 470-471, Arrowsmith Ltd. 1958;
  • a Carey-Lea filter layer is preferably interposed between the blueand green-sensitized layers.
  • Suitable light-sensitive silver halide emulsion and references describing their preparation and chemical sensitization thereof are summarized, for instance, on page 107 in section I and 111 of Product Liscensing lndex, Vol. 92, Publication 9232 (December, 1971), and include emulsions of silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide and silver chloroiodide.
  • a protective water-premeable overcoat layer such as gelatin, poly-N-vinyl lactam, gum arabic, hydrophilic copolymer of N-acrylamidoalkyl botain (ref. US. Pat. No. 2,833,650), cellulose ethers and esters, alkali soluble polyvinyl phthalate (ref. U.S. Pat. No. 2,798,004);
  • water-soluble polymers having varying degrees of solubility, such as polyvinyl alcohol (optimally with surfactant), polyvinyl pyrrolidone polyalkylene oxides, polyvinyl alcohol and its derivatives such as partial esters, ethers and acetals exemplified by hydrolyzed polyvinylacetate, polyvinyl acetaldehyde acetal, polyvinyl butyraldehyde acetal, polyvinyl sodium sulfobenzaldehyde acetal, polyvinyl disodium 2,4- disulfobenzaldehyde acetal; and water-soluble copolymers and interpolymers exemplified by copoly (methyl vinyl ether/maleic anhydride), copoly (acrylic acid/methacrylic acid ethyl ester-maleic anhydride) and copoly (maleic anhydride/acrylic acid/vinyl acetate.
  • polyvinyl alcohol optically with sur
  • the overcoat may conveniently contain an aldehyde scavenger such as described, for instance, in US. Pat. Nos. 3,236,652, 3,287,135, 3,220,839, 2,403,927 and British Patent No. 623,448, and other ingredients such as buffering agents (e.g., an acidic or basic material), and ultra-violet light absorbers such as 2,2'-d-hydroxy 4,4'-dimethoxybenzophenone, 4,4'-diazidostilbene- 2,2'-disulfonic acid sodium salt, and sodium -(a-phenylhydrazone).
  • buffering agents e.g., an acidic or basic material
  • ultra-violet light absorbers such as 2,2'-d-hydroxy 4,4'-dimethoxybenzophenone, 4,4'-diazidostilbene- 2,2'-disulfonic acid sodium salt, and sodium -(a-phenylhydrazone).
  • photographic materials and elements utilizing the present cyan-dye-forming couplers can usefully contain brightners, such as stilbenes, triazines etc. pectral sensitizing dyes supersensitizing addenda, and also absorbing and filter dyes as summarized, for instance, on page 109 in sections XlV, XV and XVI of Product Licensing lndex Volume 92 (December, 1971). J 7
  • Example 2 (Compounds No. 8 and 14) Similarly prepared were 2-amino-5-(p-chlorophenylthiomethyl phenol and 2-amino-4,6-dichloro-5-(pchlorophenylthiomethyl) phenol utilizing 2-amino phenol and 2-amin0-4,6-dichloro-phenol reactants.
  • the structures of these compounds were confired by elemental, infrared and nuclear magnetic resonance analyses and the respective melting points found to be 168-169C. and 215-216C..
  • Example 3 (Compound 15) To a stirred suspension of 40 g (0.2 mole) of sodium benzene sulfinate and 15.5 ml (0.2 mole) of formalin in 200 ml of ethanol is added a solution of 28.6 g (0.2 mole) of 2-amino-4-chlorophenol and 34.4 ml (0.4 mole) concentrated hydrochloric acid in 200 ml of ethanol. The resulting reaction mixture is stirred at room temperature for 0.5 hr. and then refluxed for 2 hr. on a steam bath. After cooling, the solid sodium chloride was filtered off and the filtrate was distilled under reduced pressure to a quarter of its original volume.
  • Example 4 Compound 16 To a stirred solution of 15.7 g (0.1 mole) of benzeneselenol and 7.6 ml (0.1 mole) of formalin in 50 ml of ethanol is added a solution of 10.9 g (0.1 mole) of o-aminophenol and 8.6 ml (0.1 mole) of concentrated hydrochloric acid in ml of ethanol. After stirring at room temperature for 0.5 hr. the mixture is refluxed for 2 hr. then cooled in an ice-bath and neutralized with sodium carbonate solution. The resulting solid is collected, washed with water and dried. The product, when recrystallized from methanol, gave 16.6 grams (60%) of white platelets identified as 2-amino-5- phenylselenomethyl phenol (m.p. 158159C.).
  • Example 6 (Compounds 1-4 and 6) having melting points at (154155C.), (-l66C.), (18l182C.), (142- 09C.) and 1 13l 14C.) are similarly prepared in accordance with the process of Examples 1 and 5.
  • Example 7 Six test film strips identified as Coatings I-6 and consisting of supported single-layer gelatinous silver bromoiodide emulsion coatings containing, per square foot of coating, 176mg silver, 450 mg gelatin, 39 mg of din-butyl phthalate as coupler solvent, and 75 mg of compounds 1-6 of this invention respectively, are exposed through a graduateddensity test object and conven tionally color developed, washed, bleached, washed, fixed, washed and dried. The dyes produced in proportion to the reproduced image are then spectrophotometrically evaluated and the results tabulated in the Table ll below:
  • R and R each are a hydrogen atom, a halo group, an aryl group, an alkyl group or an alkoxy group;
  • R is an aryl group
  • R is a hydrogen atom or a coupling-off group
  • R is a hydrogen atom or an alkyl group
  • X is a bivalent group of the formulae --S-,
  • R is a phenoxyalkylcarbonyl group or a hydrogen atom; R is a hydrogen atom or an alkyl group of one to three carbon atoms; 5 R and R are individually defined as a hydrogen atom or a chloro group; R is phenyl or a chlorophenyl group; and R is a hydrogen atoms or a coupling off group.
  • X is R is a hydrogen atom, an alkyl group of one to 22 carbon atoms or a radical of the formula in which R, is an alkyl group of one to 20 carbon atoms, an alkylamino group of one to 20 carbon atoms, a
  • phenylamino group a naphthylamino group, a phenyl group or a naphthyl group
  • R and R are each a hydrogen atom, a halo group
  • a phenyl group a naphthyl group, an alkyl group,
  • R' is a phenyl group or a naphthyl group; and R, is a hydrogen atom, a halo group, a thiocyano group, a phenoxy group, .or an alkoxy group of one to 20 carbon atoms.
  • R is a hydrogen atom, an-alkyl group, an aryl group.
  • R and R each are a hydrogen atom, a halo group, an aryl group, an alkyl group or an alkoxy group;
  • R is an aryl group
  • R is a hydrogen atom or a coupling-off group
  • R is a hydrogen atom or an alkyl group
  • X is a bivalent group of the formulae S or Se.
  • X is R is a phenoxyalkylcarbonyl group or a hydrogen atom;
  • R- is a hydrogen atom or an alkyl group of one to three carbon atoms
  • R and R are individually defined as a hydrogen atom or a chloro group
  • R is phenyl or a chlorophenyl group
  • R is a hydrogen atom or a coupling off group.
  • a color photographic element comprising a support layer having at least one silver halide emulsion layer and containing a phenolic cyan dye-forming color photographic coupler of the formulae wherein R, is a hydrogen atom, an alkyl group of 1-22 carbon atoms or a radical of the formula in which R',, is an alkyl group of one to 20 carbon atoms, an alkylamino group of l-20 carbon atoms, a phenylamino group, a naphthylamino group, a phenyl group or a naphthyl group; R, and R, are each a hydrogen atom, a halo group, a phenyl group, a naphthyl group, an alkyl group, or an alkoxy group wherein the alkyl moieties thereof contain one to 15 carbon atoms; R',, is a phenyl group or a naphthyl group; and R, is a hydrogen atom, a halo
  • a color photographic element comprising a support ahving at least onesilver halide emulsion layer containing a cyan dye-forming coupler of the formula 20.
  • a color photographic element comprising a support having at least one silver halide emulsion layer containing a cyan dye-forming coupler of the formula 21.
  • a color photographic element comprising a support having at least one silver halide emulsion layer containing a cyan dye-forming coupler of the formula 4 NH 0 lE-O-Q-CBHM: @SOr-CH 51111-1;
  • a color photograhpic element comprising a support having at least one silver emulsion layer containing a cyan dye-forming coupler of the formula Cl-Q- S-CHi 23.
  • a color photographic element comprising a support having at least one silver halide emulsion layer containing a cyan dye-forming coupler of the formula I G Brit CI NHCOH-O- Odin-l,
  • a color photographic element comprising a support having at least one silver halide emulsion layer containing a cyan dye-forming coupler of the formula -NH O 0 3 QCJLH: erg s on, sHn-t or Se.
  • R is phenyl or a chlorophenyl group and R, is a hydrogen atom, a chloro group, a thiocyano group, a phenoxy group or an alkoxy group having one to 12 carbon atoms.
  • R is a hydrogen atom; R, is a hydrogen atom or an alkyl group of one to three carbon atoms.

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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US00223375A 1972-02-03 1972-02-03 Phenol color couplers Expired - Lifetime US3779763A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880661A (en) * 1971-12-29 1975-04-29 Eastman Kodak Co Silver halide emulsion containing acylamidophenol photographic couplers
US4009035A (en) * 1974-01-25 1977-02-22 Konishiroku Photo Industry Co., Ltd. Process for forming cyan dye photographic images
US4940812A (en) * 1989-07-17 1990-07-10 Eastman Kodak Company 5-substituted aminophenols
US5043469A (en) * 1989-07-17 1991-08-27 Eastman Kodak Company Process for preparing 5-substituted aminophenols
EP0574090A1 (en) 1992-06-12 1993-12-15 Eastman Kodak Company One equivalent couplers and low pKa release dyes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443536A (en) * 1981-08-25 1984-04-17 Eastman Kodak Company Nondiffusible photographic couplers and photographic elements and processes employing same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2369929A (en) * 1943-03-18 1945-02-20 Eastman Kodak Co Acylamino phenol couplers
US3620745A (en) * 1968-04-01 1971-11-16 Eastman Kodak Co Color photographic silver halide emulsions of different developing speed one layer having a dir coupler

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2369929A (en) * 1943-03-18 1945-02-20 Eastman Kodak Co Acylamino phenol couplers
US3620745A (en) * 1968-04-01 1971-11-16 Eastman Kodak Co Color photographic silver halide emulsions of different developing speed one layer having a dir coupler

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880661A (en) * 1971-12-29 1975-04-29 Eastman Kodak Co Silver halide emulsion containing acylamidophenol photographic couplers
US4009035A (en) * 1974-01-25 1977-02-22 Konishiroku Photo Industry Co., Ltd. Process for forming cyan dye photographic images
US4940812A (en) * 1989-07-17 1990-07-10 Eastman Kodak Company 5-substituted aminophenols
WO1991001300A1 (en) * 1989-07-17 1991-02-07 Eastman Kodak Company 5-substituted aminophenols
US5043469A (en) * 1989-07-17 1991-08-27 Eastman Kodak Company Process for preparing 5-substituted aminophenols
EP0574090A1 (en) 1992-06-12 1993-12-15 Eastman Kodak Company One equivalent couplers and low pKa release dyes

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GB1407922A (en) 1975-10-01
FR2170168A1 (enExample) 1973-09-14
FR2170168B1 (enExample) 1975-10-31
CA1012547A (en) 1977-06-21
BE794956A (fr) 1973-08-02

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