US3556796A - Silver halide emulsion containing naphthol colour couplers for cyan - Google Patents

Silver halide emulsion containing naphthol colour couplers for cyan Download PDF

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Publication number
US3556796A
US3556796A US585730A US3556796DA US3556796A US 3556796 A US3556796 A US 3556796A US 585730 A US585730 A US 585730A US 3556796D A US3556796D A US 3556796DA US 3556796 A US3556796 A US 3556796A
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United States
Prior art keywords
group
radical
colour
silver halide
cyan
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US585730A
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English (en)
Inventor
Hector Alfons Vanden Eynde
Marcel Karel Van Doorselaer
Arthur Henri De Cat
Rigobert Otto
Friedrich-Wilhelm Kunitz
Walter Schulte
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • 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
    • G03C7/18—Processes for the correction of the colour image in subtractive colour photography
    • 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
    • G03C7/344—Naphtholic couplers

Definitions

  • the color couplers have the structure s Oz-Y wherein Z is a hydrogen atom or a halogen atom, X is a halogen atom, an alkyloxy group, an alkylthio group, an alkylsulfonyl group, an aryloxy group, an
  • arylthio group an arylsulfonyl group, a monoalkylamino group, a dialkylamino group or an aminogroup, the nitrogen atom of which makes part of the ring atoms of a saturated he'terocyclic nucleus,
  • Y is an alkyl radical, a monoalkylamino group, a dialkylamino. group or an amino group, the nitrogen atom of which makes part of the ring atoms of a saturated heterocyclic nucleus, at least one of thealkyl radicals in the above groups being an aliphatic radical containing from to 20 carbon atoms.
  • This invention relates to colour photography and the production of photographic colour images by colour de- 2 Claims 3,556,796 1. Patented m 1 1971:
  • alkaline potassium hexa- ,...-jcyanoferrate(III) bleaching bath in the presence of a compound that oxidativelY-couples with the residual colour couplerthereby forming a secondarydye'image'having a gradationopposite to that of said primary dye image and absorbing light in at least onevof said regions, whereliz-inthe primary dye imageundesirably absorbsybut'transvelopment.
  • a compound that oxidativelY-couples with the residual colour coupler thus forming a secondarydye'image'having a gradationopposite to that of said primary dye image and absorbing light in at least onevof said regions, whereliz-inthe primary dye imageundesirably absorbsybut'transvelopment.
  • It relates more particularly to -novel cyan forming colour couplers suitable for use in negative silver halide colour materials and tothe use ofv said colourforming couplers in an integral mask process.
  • the cyanforming colour couplers should yield on development a dye that absorbs light with a wavelength from 700 to 600 m (red light). In practice, however, there should be reckoned with more or less considerable side-absorptions in the colour regions of 600500 m (green light) and 500-400 mg (blue light).
  • Cyan-formingcolour couplers have now been found that possess the property of forming by coupling with an oxidized developing agent (in the areas of the exposed and reduced silver halide) a cyan dye image of intense colour density and high gradation, which image absorbs light in-the green and blue region of the spectrum only to a very small extent, said couplers being at the same time 7 able to form very easily a bright masking dye image by oxidative coupling according to the above described procvery high concentration without giving rise to flocculation.
  • an oxidized developing agent in the areas of the exposed and reduced silver halide
  • the cyan-forming colour couplers according to the present invention may be represented the following general formula: "1 W t wherein:
  • Z represents a hydrogen atom, or a halogen atom, e.g. a chlorine atom,
  • X represents a halogen atom, e.g. a chlorine or fluorine atom, a --OR group, a SR group, at 40 11 group, a -aryl group, a S-aryl group, a -SO -aryl group including the latter three groups wherein the aryl radi'cal is substituted or a group, wherein R represents an alkyl group or an aralkyl group, e.g. a lbenzyl group or phenylethyl group, R represents a hydrogen atom, an alkyl group, or an aralkyl group, e.g.
  • R and R together represent the atoms necessary to close a cycloaliphatic or saturated hetero- .cyclic nucleus, such as a morpholine or piperidine nucleus, and
  • Y represents an alkyl radical, an araikyl radical, a fluorosubstituted alkyl radical or a s I f R, radical, wherein R, represents an alkyl group or an aralkyl group such as a benzyl group, and R'g represents a hydrogen atom, an alkyl group, an aralkyl group, e.g. a benzylgroup, or R, and -R' together represent the atoms necessary to close a saturated heterocyclic nucleus, such as a morpholine or piperidine nucleus at least one of the R R R' and R' radicals representing an aliphatic radical for making the molecule fast to diffusion, e.g. an alkyl radical containing from to 20 carbon atoms, preferably containing 12 to 18 carbon atoms.
  • R represents an alkyl radical, an araikyl radical, a fluorosubstituted alkyl radical or a s I f R
  • R and R represents an alkyl radical
  • Y represents a I OH Cl SOrN"(CH2) 5CHa 4 II on Fl C0-NH- son (oul)w-ont III (H1 0011:;
  • COJNHQ' (OH CH l 2)1s a SO2N ⁇ 1 V In on: H2C ⁇ /CH2 R t @130 0-NH /GH:4 SO2N ⁇ (OH:-)15 0H3 V: on 11 3o morn-Q SO2NH(GHz)
  • PREPARATION 2 (a) 2 methoxy 5 methyl-n-hexadecylaminosulphonylbenzene
  • a solution of 192 g. of 2-chloro-5-methyl-n-hexadecylaminosulphonyl-nitrobenzene, prepared as described above, and of 22.7 g. of sodium methylate in 1200 cos. of methanol is refluxed for 30 minutes.
  • the reaction mixture 12 is freed from sodium chloride by filtration.
  • the filtrate is allowed to cool and a yellow crystalline product precipitates, which is collected by filtration and dried. Yield: 181 g. (96%). Melting point: 68 C.
  • the crude product is added to 100 ml. of ethylene glycol monornethyl ether and treated at 70 C. for 15 h. with 42.6 g. of methyl iodide whereupon the warm solution is filtered. The precipitate formed in the filtrate is separated by suction and washed with methanol. Yield: 32.5 g. (73.5%). Melting point: 105 C.
  • vinylene homologues phenylene homologues or azavinylene homologues which contain the vinylene grouping, the phenylene radical or the azornethine group in the above formula between the carbonatom and the amino group. :I .i
  • mask-forming compounds are preferably used which correspond, to the following general formulae:
  • R represents a radical of the formula '-CONH or SO X'wherein X represents a hydroxyl radical an amino radical, a substituted amino radical such as a- .dialkylarnino radical, a heterocyclic radical such as a 'N-morpholinyl radical or a N-piperidyl radical, an alkyl radical, e.g. a methyl radical or a hexadecyl radical, a substituted alkyl radical, an aryl radical or a substituted aryl radical, e.g.
  • a methoxy-, or a hexadecyloxy-su-bstituted phenyl radical a carbethoxy-sub stituted phenyl radical, an alkyl-substituted phenyl radical such as a tolyl radical, a sulphonic acid-substituted phenyl radical, a sulphonic acid ester-sub-.
  • stituted phenyl radical, a sulpharnoyl-substituted phenyl radical, a halogen-substituted phenyl radical e.g.
  • I V t R represents a hydrogen atom, an alkyl radical such as a methyl or hexadecyl radical, an allyl radical,- an
  • aralkyl radical e.g. a benzyl radical, an aryl radical e.g. phenyl or naphthyl, a substituted aryl radical eig.
  • l R represents a hydrogen atom, an alkyl methyl or a hexadecyl radical, a substituted alkyl radical, an aralkyl radical, e.g. a benzyl radical, an aryl radical, e.g. phenyl or naphthyl, and a substituted aryl radical, e.g. a methoxy-su bstituted phenyl radical,
  • an aralkyl radical e.g. abenzyl radical, a substituted benzyl radical such asa methoxy-su bstituted benzyl radical, an alkenyl radical e.g. an allyl radical, an aryl radical, a substituted aryl radical, e.g.a monoor dihalogen-substituted phenyl radicaL. a hydroxy-sub-- stituted phenyl radical, an 'alkoxy-substituted 'phenyl, radical, e.g.
  • aralkyl radical e.g. abenzyl radical, a substituted benzyl radical such asa methoxy-su bstituted benzyl radical, an alkenyl radical e.g. an allyl radical, an aryl radical, a substituted aryl radical, e.g.a monoor dihalogen-substituted phenyl
  • a monoor dirnethoxyphenyl radical or a hexadecyloxyphenyl radical an alkylthiophenylphenyl radical, an acyloxyphenyl radical, e.g. a'palrnitoyloxy: phenyl radicaL'an acylaminophenyl radical, a dialkyl- 'arninophenyl radical, an alkyl'sulphonylphenyl radical,
  • heterocyclic radical e.g. a furyl radical, a thienyl radical, a pyridyl radical or a 5-1,3-benzodioxylyl radical,-
  • R' represents a -CONH or SO X radical, wherein X has the same value as described for R each of R' and R';, represents an alkyl, aralkyl or aryl radical, which may be substituted,
  • Z represents the non-metallic atoms necessary to complete a 6-membered aromatic ring, which may be substituted.
  • the mask-forming compounds are preferably incorporated in the photographic material in a form resisting to diffusion. Therefore they contain in their structure a long aliphatic carbon chain preferably a carbon chain having from 5 to 20 carbon atoms in a straight line.
  • a non-migratory cyanforming colour coupler according to the above general formula and preferably also a masking compound that oxidatively couples with said colour coupler in an alkaline oxidizing bleaching bath are homogeneously mixed in dissolved state with a light-sensitive silver halide emulsion, preferably immediately before the coating of the emulsion. They may, however, also be added to the composition of a water-permeable non-light-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 water-permeable nonlight-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 cyan-forming colour couplers described in the present invention are usually incorporated into a redsensitized silver halide emulsion. According to a common procedure in the art, this silver halide emulsion is coated asthe first colour coupler-containing layer of a photographic multilayer colour material.
  • a photographic multilayer colour material usually consists in the given sequence of a support, a red-sensitized silver halide emulsion layer with a cyan-forming colour coupler, a green-sensitized silver halide emulsion layer with a magenta-forming colour coupler and a blue-sensitive silver halide emulsion layer with a yellow-forming colour coupler.
  • the support of this multilayer material preferably consists of a transparent material e.g. glass, cellulose nitrate, a cellulose ester such as cellulose triacetate, polyester, polystyrene or another synthetic or natural resin.
  • a yellow filter layer generally comprising colloidal silver dispersed in gelatin is usually provided between the silver halide emulsion layer containing the yellowforming colour coupler and the green-sensitized silver halide emulsion layer.
  • the cyan-forming colour couplers according to the present invention may also be applied in so-called mixedgrain type and mixed packet type emulsions, as e.g. described in the United States patent specifications 2,592,243 by B. H. Carroll and W. T. Hanson, issued Apsr 8, 1952 and 2,698,794 by L. Godowsky, issued J an. 4, 19
  • the exposed silver halide emulsion layer is developed with an aromatic primary amino developing substance in the presence of a cyan forming colour coupler according to the present invention.
  • Aromatic primary amino compounds such as p-phenylenediamine and derivatives such as N,N-diethyl-p-phenylenediarnine, N,N-diethyl N sulphomethyl p phenylenediamine and N,N-diethyl N carboxymethyl p phenylenediamine are commonly used.
  • the cyan-forming colour couplers according to the present invention form cyan dyes having an absorption spectrum that makes these colour couplers, as already mentioned, apt to be used in negative material.
  • the emulsion After adding the necessary stabilizing, hardening and wetting agents the emulsion is coated onto 10 sq. m. and dried.
  • This material is rinsed for 30 minutes at 18 to 20 C. and fixed for 5 minutes at 20 C. in a fixing bath of the following composition:
  • a primary cyan dye imagetogether with a secondary orange-red mask image of opposite gradation to the said primary dye image is formed.
  • the emulsion After neutralizing and adding the necessary stabilizing, hardening and wetting agents the emulsion is coated onto sq. m. and dried.
  • a primary cyan dye image together with a secondary orange-red mask image of opposite gradation to the said primary dye image is formed.
  • the emulsion After neutralizing and adding the necessary stabilizing, hardening and wetting agents, the emulsion is coated onto 10 sq. m. of support and dried.
  • Example 2 After processing as described in Example 1 a primary cyan dye image together with a secondary mask image of opposite gradation is obtained.
  • the colour of said mask image lies between orange and magenta which are the colours obtained respectively when using the masking compounds separately.
  • a light-sensitive silver halide photographic material containing in a light-sensitive silver halide emulsion a non-diffusing coupler of the general formula:
  • Z is a hydrogen atom or a halogen atom
  • X is a halogen atom, an alkyloxy group, an alkylthio group, an alkylsulfonyl group, an aryloxy group, an arylthio group, an arylsulfonyl group, a monoalkylamino group, a dialkylamino group, or an amino group the nitrogen atom of which makes part of the ring atoms of a saturated heterocyclic nucleus, and
  • Y is an alkyl radical, a monoalkylamino group, a dialkylamino group or an amino group, the nitrogen atom of which makes part of the ring atoms of a saturated heterocyclic nucleus, at least one of the alkyl radicals in the above groups being an aliphatic radical containing from 5 to 20 carbon atoms;
  • X is a methoxy group, or a dialkylamino group
  • Y is a monoalkylamino group, or a dialkylamino group, 5 at least one of the allgylradicals in the said formula ing a1kyl radca1 having from 5 jo 20 carbon omega-straight line; r

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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US585730A 1965-10-13 1966-10-11 Silver halide emulsion containing naphthol colour couplers for cyan Expired - Lifetime US3556796A (en)

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Application Number Priority Date Filing Date Title
GB43386/65A GB1104729A (en) 1965-10-13 1965-10-13 Colour couplers for cyan

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US3556796A true US3556796A (en) 1971-01-19

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US (1) US3556796A (enEXAMPLES)
BE (1) BE688180A (enEXAMPLES)
CH (1) CH472056A (enEXAMPLES)
FR (1) FR1496512A (enEXAMPLES)
GB (1) GB1104729A (enEXAMPLES)
NL (1) NL6614341A (enEXAMPLES)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844795A (en) * 1971-05-07 1974-10-29 Agfa Gevaert Ag Silver halide photographic material containing azo masking couplers
US3869291A (en) * 1970-12-08 1975-03-04 Agfa Gevaert Ag Silver halide light-sensitive color photographic material containing color coupler masking compound and development inhibitor releasing compound
US4250251A (en) * 1978-07-27 1981-02-10 Eastman Kodak Company Phenylsulfamoyl couplers, coupler compositions and photographic elements suited to forming integral sound tracks
US4957853A (en) * 1985-10-08 1990-09-18 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material containing cyan coupler and method for use thereof
US5476757A (en) * 1994-12-19 1995-12-19 Eastman Kodak Company Photographic element containing a novel cyan dye forming coupler and process for its use
US5508148A (en) * 1994-12-19 1996-04-16 Eastman Kodak Company Photographic element containing a novel cyan dye forming coupler and process for its use

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1099288A (en) * 1978-07-27 1981-04-14 Harland J. Osborn Phenylsulfamoyl couplers, coupler compositions and photographic elements suited to forming integral sound tracks
DE3535247A1 (de) * 1985-10-03 1987-04-09 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial mit leicht dispergierbaren farbkupplern

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3869291A (en) * 1970-12-08 1975-03-04 Agfa Gevaert Ag Silver halide light-sensitive color photographic material containing color coupler masking compound and development inhibitor releasing compound
US3844795A (en) * 1971-05-07 1974-10-29 Agfa Gevaert Ag Silver halide photographic material containing azo masking couplers
US4250251A (en) * 1978-07-27 1981-02-10 Eastman Kodak Company Phenylsulfamoyl couplers, coupler compositions and photographic elements suited to forming integral sound tracks
US4957853A (en) * 1985-10-08 1990-09-18 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material containing cyan coupler and method for use thereof
US5476757A (en) * 1994-12-19 1995-12-19 Eastman Kodak Company Photographic element containing a novel cyan dye forming coupler and process for its use
US5508148A (en) * 1994-12-19 1996-04-16 Eastman Kodak Company Photographic element containing a novel cyan dye forming coupler and process for its use

Also Published As

Publication number Publication date
GB1104729A (en) 1968-02-28
NL6614341A (enEXAMPLES) 1966-12-27
CH472056A (de) 1969-04-30
FR1496512A (fr) 1967-09-29
BE688180A (enEXAMPLES) 1967-04-13

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