US3287132A - Silver dye bleach dyestuffs and their use in colour photography - Google Patents

Silver dye bleach dyestuffs and their use in colour photography Download PDF

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Publication number
US3287132A
US3287132A US306685A US30668563A US3287132A US 3287132 A US3287132 A US 3287132A US 306685 A US306685 A US 306685A US 30668563 A US30668563 A US 30668563A US 3287132 A US3287132 A US 3287132A
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parts
dye
layer
silver
solution
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US306685A
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Hunt Francis George
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Ilford Imaging UK Ltd
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Ilford Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/039—Disazo dyes characterised by the tetrazo component
    • C09B35/04—Disazo dyes characterised by the tetrazo component the tetrazo component being a benzene derivative
    • 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
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
    • G03C7/29—Azo dyes therefor

Definitions

  • a photographic silver halide emulsion layer usually a gelatino silver halide emulsion layer, includes as a uniform dispersion therein, a. suitable dyestulf.
  • a latent silver image is formed in the layer and is developed to a silver image.
  • the layer is then treated with a bleach bath which has the effect of oxidising the silver image and simultaneously reducing (bleaching) the dyestutt in the region of the silver image.
  • the silver salts and any residual silver are then removed and the layer then contains only a dyestuff image which is complementary in sign to the original silver image.
  • the layer may be dyed with the dyestufl after the exposure step or after the development of the silver image, or the dyestufi may be included in a plain gelatin layer coated adjacent to the emulsion layer.
  • a multilayer material which contains three light-sensitive silver halide emulsion layers, one sensitive to blue light only and the other sensitised to green and red light respectively.
  • a blueabsorbing filter layer between these latter layers and the emulsion which is sensitive only to blue, a common form of assembly being:
  • Layer (d) is not always essential since layer (e), when dyed yellow, may provide a sufiicient barrier to blue light.
  • Polychromatic light incident on layer (e) causes the formation of latent silver images in layers (e), (c) and (b), respectively recording in those layers the blue, green and red sensations of the exposing light.
  • layer (b) is dyed blue-green (cyan)
  • layer (c) is dyed magenta
  • layer (e) is dyed yellow. Accordingly, when the material is exposed, developed to form silver images and subjected to the required bleaching treatment and treated to remove residual silver salts and silver, the final product carries positive yellow magenta and cyan images complementary to the -negative silver images formed on development, so that when viewed it provides an accurate representation of the original subject of the exposure.
  • a principal difliculty associated with the process is to ensure that the dyestufi employed will not diffuse from the gelatin emulsion layer in which it is incorporated, and various proposals, such as mordanting, have been made to overcome this difliculty.
  • dyestuffs for use, moreover, it is desirable that they should be bleached rapidly by the bleaching baths employed and also important that their inclusion in the emulsion layer should not too seriously reduce the sentitivity of the emulsion.
  • the dye should approach as closely as possible to the theroetical requirement that, of red, blue and green light, it should absorb all of one while fully transmitting or reflecting both of the others.
  • cyan dyestufi's of the general Formula I According to a first feature of the present invention there are provided cyan dyestufi's of the general Formula I.
  • X is halogen, hydroxyl, amino, substituted amino or hydrogen
  • the ring W is unsubstituted orcarries one or more substituents selected from halogen, alkyl, alkoxy, sulphonic acid and alkali metal sulphonate, the number of sulphonic acid or sulphonate groups in the ring W being not greater than 1
  • U is hydrogen, sulphonic acid or alkali metal sulphonate
  • V is hydrogen or the grouphe and R and R are hydrogen, alkyl, substituted alkyl (e.g.
  • the aforesaiddyes may be prepared by the method in which the diazotised p-nitroaniline derivative (or paminoacetanilide derivative) is coupled to the first naphthalene component, the monoazo compound is reduced (or hydrolysed), re-diazotised and coupled to the second naphthalene component.
  • a process for the production of a cyan dyestulf image in a photographic layer comprises including in a light-senstive gelatino silver halide emulsion layer, or in a plain gelatin layer coated adjacent thereto, a cyan dyestuff of the general Formula I, forming a latent silver image in said layer, developing said image, subjecting the developed image to treatment which bleaches or removes the silver image and simultaneously bleaches the dyestulf in situ therewith, and removing any residual silver and silver salts from the product.
  • the invention further includes photographic materials which comprise a sheet support and a photographic silver halide emulsion layer, the said layer, or a layer adjacent thereto, including a cyan dyestutf of general Formula I.
  • the invention includes photographic materials which comprise, in superposition on a sheet support, a .layer of a photographic silver halide emulsion layer sensitive to blue light, a layer of a photographic silver halide emulsion layer sensitised to green light and a layer of a photographic silver halide emulsion layer sensitive to red light, the said layers selectively containing yellow, magenta and cyan dyes, the cyan dye being a dye of general Formula I. V
  • Diazotisation is essentially complete when an excess of nitrous acid is still detectable by means of starch/iodide test paper, fifteen minutes after; the last addition of sodium nitrite. The excess nitrous-acid is destroyed by adding a sufiicient amount of sulphamic acid. The diazotisation solution is filtered to remove a trace of insoluble matter.
  • . xan tbe precipitated disazo dye is filtered off.
  • the paste dye is stirred with 600 parts of water at 60 C. and 60 parts of common salt added to precipitate the dye.
  • the dye is filtered olf and washed on the filter with potassium acetateliquor until the dye is free from-chloride. I
  • the dye is finally washed with 200 parts of isopropanol and.
  • the 1- amino-8-naphthol-3:6-disulphondiethylamide may be prepared by the method described in specification No. 615,606. 1
  • the 1-amino-8-naphthol-3:6-disulphonethylamide may be prepared in an analogous manner to the method of'spec ification No'.-6l-5',606.. r a? if r methylamide is used in place of the 1-amino-8-naphtholdye.
  • the 1-amino-8-naphthol-4:6-disulphonethylamide may be prepared in an analogous manner to the methods of specifications Nos. 326,226 and 615,606.
  • the dye is prepared in a similar way to that described in Example 2 except that 5.36 parts of l-amino-S-naphthol-4:6 disulphondiethylamide is used in place of 1- amino-8-naphtho1-3:6-disulphonmethylamide. There results 10.7 parts of dye.
  • the 1-amino-8-naphthol-4:6 disulphondiethylarnide may be prepared in an analogous manner to the methods of specifications Nos. 326,226 and 615,606.
  • the slurry of diazotised aminomonoazo compound is added dropwise to the stirred solution of l-amino-S-naphthol-3:6disulphondiethylamide at 05 C. over 1 hour. After stirring for a further one hour the mixture is heated to C. and stirred at 90 C. for 1 hour. The mixture is cooled to 60 C. and 9.5 parts 31% sodium hydroxide liquor is added. The mixture is filtered and washed on the filter with 5% brine made alkaline to Clayton Yellow test paper with sodium hydroxide. The paste dye is slurried with 5% potassium acetate solution, neutralised by adding acetic acid and refiltered. The paste dye is finally washed on the filter with 74 OP industrial meth-.
  • the paste aminomonoazo compound is dissolved in 125 parts of water by adding 6.7 parts of 31% sodium hydroxide liquor and cooled to below 5 C. 14.5 parts of 32% hydrochloric acid is added and diazotisation is elfeoted by the dropwise addition of a solution of 1.11 parts of sodiium nitrite dissolved in 7 parts of water at below 5 C.
  • the slurry of the. diazomonoazo compound is added 'dropwise to the stirred solution of 1-amino-8-naphthol- 3:6-disulphondiethylamide over minutes at below 5 C.
  • the mixture is stirred for a further 15 hours, heated to 80 C. and 2 par-ts of sodium carbonate is added.
  • precipitated dye is filtered off and crystallised from. 500 parts of 2 /2 brine.
  • the crystallised dye is washed with 25% potassium acetate solution'and then 'washed 'with methylated spirit.
  • the dye is dried at 40 C. There results 11.1 parts of dye.
  • a process ofv colour photography comprises a process as set forth above in which the gelatino silver halide layer is red-sensitive and constitutes one of the layers of a multilayer photographic material which further contains photographic emulsion -layerssensitive to green and blue light and respectively dyes with magenta and yellow dyestuffs, and the said cyan dyesturf is included insaid red-sensitive layer or in a plain gelatin layer. coated adjacent thereto.
  • the invention provides a process in which the said cyan dyed layer is layer (b) of an'assembly consisting of:
  • Upportlayer g p Red-sensitive emulsion layer dyed cyan
  • Blue-absorbing filter layer I Blue-sensitive emulsion layer dyed yellow, optionally with plain colloid separating layers between some or all of the adjacent layers recited.
  • the invention further includes such light-sensitive materials employed in the aforesaid processes,- and suitable for variants of those processes, which consist of or include a gelatino silver halide emulsion layer containing a cyan dyestuff as above set forth.
  • the bleaching of, the cyan dyestuffs employed in'this invention can be effected by anyof the types of bleaching :bath commonly employed in the silver-dye-bleach process.
  • the plain use of acid, e.g. hydrobromic or. hydrochloric, is effective but isvery slow.
  • the inclusion of halide salts has an accelerative effect, but these bleaching bathsare 'still slow.
  • the inclusion of a solvent for silver halide such as thiourea or pyridine has a strongly accelerative effr'ect, and this can be greatly increased by the inclusion of an accelerating substance or catalyst.
  • Thefollowing table shows examples of further nents and the dyes are prepared by a'method essentially dyes: suitable for incorporation in'a red sensitive photographic layer as exemplified by Example 9.
  • the table lists the :components of the dyes as first, middle and end compo- 1st component Middle component End component 1. lzs dihydroxynaph 6-nitro-3amino-4- 1amino8-napliththalene-3 :6-disul octyloxy-l-methyl L 01-3 6-disulphon- .phonie acid.. benzene. diethylamide.
  • naphthalene-3 6- methoxy-l-methyl disulphom'c acid. benzene. v
  • thaene-medisulphonic 1 aci 7. 1:8-dihydroxynaphdo l-naphthoM-sulthalene-3:6- disulphonic phondiethylacid; amide.
  • a photographicsilver halide emulsion .layer which comprises including in contact with said emulsion a cyan dyestuff selected from the class consisting of dyestufis of the formula:
  • R and R taken separately are each selected from the class consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, aralkyl and aryl and taken together constitute, with the nitrogen atom to which they are attached, a cyclic grouping, and the said dyestuffs in which the ring W carries at least one substituent selected from the class consisting of halogen, alkyl, alkoxy, sulphonic acid and alkali metal sulphonate, the number of sulphonic groups in the ring W being not greater than 1, forming a latent silver image in said emulsion layer, developing said image, subjecting the developed image to treatment which bleaches the silver image and simultaneously bleaches the said dyestutf in situ therewith, and removing any residual silver and silver salts from the product.
  • a photographic material which comprises a sheet support and a photographic silver halide emulsion layer, including in contact with said emulsion a cyan dyestutf selected from the class consisting of dyestuffs of the formula:
  • X is selected from the class consisting of halogen, hydroxyl, amino, substituted amino and hydrogen
  • U is selected from the class consisting of hydrogen, sulphonic acid and alkali metal sulphonate
  • V is selected from the class consisting of hydrogen and the grouping:
  • R and R taken separately are each selected from the class consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, aralkyl and aryl and taken together constitute, with the nitrogen atom to which they are attached, a cyclic grouping, and the said dyestufis in which the ring W carries at least one substituent selected from the class consisting of halogen, alkyl, alkoxy, sulphonic acid and alkali metal sulphonate, the number of sulphonic groups in the ring W 'being not greater than 1.
  • a photographic material which comprises a sheet support and, in superposition thereon, a layer of a photographic silver halide emulsion sensitive to blue light, a layer of a photographic silver halide emulsion sensitive to green light and a layer of a photographic silver halide emulsion sensitive to red light, the said layers selectively containing, yellow, magenta and cyan dyes and the cyan dye being a dye of the formula:
  • R and R taken separately are each selected from the class consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, aralkyl and aryl and taken together constitute, with the nitrogen atom to which they are attached, a cyclic grouping, and the said dyestufis in which the ring W carries at least one substituent selected from the class consisting of halogen, alkyl, alkoxy, sulphonic acid and alkali metal sulphonate, the number of sulphonic groups in the ring W being not greater than 1.
  • cyan dye is a dye of the formula:
  • cyan dye is a dye of the formula:
  • a photographic material according to claim 3 wherein the cyan dye is a dye of the formula:
  • cyan dye is a dye of the formula:
  • cyan dye is a dye of the formula:
  • cyan dye is a dye of the formula:
  • a photographic material according to. claim, 3 wherein the cyan dye is a dye of the formula:

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Coloring (AREA)
US306685A 1962-09-24 1963-09-05 Silver dye bleach dyestuffs and their use in colour photography Expired - Lifetime US3287132A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB36242/62A GB1028562A (en) 1962-09-24 1962-09-24 Disazo dyestuffs and their use in colour photography

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US3287132A true US3287132A (en) 1966-11-22

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US (1) US3287132A (de)
BE (1) BE637793A (de)
CH (1) CH440962A (de)
DE (1) DE1252058B (de)
GB (1) GB1028562A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3454401A (en) * 1964-02-13 1969-07-08 Ciba Ltd Photographic material for the silver dyestuff bleaching process
US3503741A (en) * 1966-11-04 1970-03-31 Eastman Kodak Co Silver-dye-bleach process utilizing formazan dyes

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1975609A (en) * 1931-11-06 1934-10-02 Ici Ltd Azo dye and method for its preparation
GB615606A (en) * 1946-12-30 1949-01-07 Walter Francis Beech New azo dyestuffs
CA479607A (en) * 1951-12-18 Gaspar Bela Azo dyes for color photography
US2612448A (en) * 1948-04-02 1952-09-30 Gaspar Photographic elements containing azo dyes and process using them
US2779758A (en) * 1951-09-04 1957-01-29 Saul & Co Chromable disazo dyestuffs
US3038802A (en) * 1957-04-29 1962-06-12 Ilford Ltd Photographic color element with novel cyan dye
US3211554A (en) * 1960-07-22 1965-10-12 Ciba Geigy Corp Photographic layers for the silver dyestuff bleaching method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA479607A (en) * 1951-12-18 Gaspar Bela Azo dyes for color photography
US1975609A (en) * 1931-11-06 1934-10-02 Ici Ltd Azo dye and method for its preparation
GB615606A (en) * 1946-12-30 1949-01-07 Walter Francis Beech New azo dyestuffs
US2612448A (en) * 1948-04-02 1952-09-30 Gaspar Photographic elements containing azo dyes and process using them
US2779758A (en) * 1951-09-04 1957-01-29 Saul & Co Chromable disazo dyestuffs
US3038802A (en) * 1957-04-29 1962-06-12 Ilford Ltd Photographic color element with novel cyan dye
US3211554A (en) * 1960-07-22 1965-10-12 Ciba Geigy Corp Photographic layers for the silver dyestuff bleaching method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3454401A (en) * 1964-02-13 1969-07-08 Ciba Ltd Photographic material for the silver dyestuff bleaching process
US3503741A (en) * 1966-11-04 1970-03-31 Eastman Kodak Co Silver-dye-bleach process utilizing formazan dyes

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GB1028562A (en) 1966-05-04
DE1252058B (de)
BE637793A (de)
CH440962A (de) 1967-07-31

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