US3038802A - Photographic color element with novel cyan dye - Google Patents

Photographic color element with novel cyan dye Download PDF

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Publication number
US3038802A
US3038802A US800639A US80063959A US3038802A US 3038802 A US3038802 A US 3038802A US 800639 A US800639 A US 800639A US 80063959 A US80063959 A US 80063959A US 3038802 A US3038802 A US 3038802A
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US
United States
Prior art keywords
parts
layer
cyan
silver
acid
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
US800639A
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English (en)
Inventor
Kelier Ernst
Jung Jean-Pierre
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.)
Ilford Imaging UK Ltd
Original Assignee
Ilford Ltd
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
Priority to BE567189D priority Critical patent/BE567189A/xx
Priority claimed from GB1359857A external-priority patent/GB847527A/en
Priority to US728065A priority patent/US3002964A/en
Priority claimed from US728065A external-priority patent/US3002964A/en
Priority to FR1205587D priority patent/FR1205587A/fr
Priority to DEG24411A priority patent/DE1077531B/de
Application filed by Ilford Ltd filed Critical Ilford Ltd
Priority to US800639A priority patent/US3038802A/en
Application granted granted Critical
Publication of US3038802A publication Critical patent/US3038802A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/025—Disazo dyes containing acid groups, e.g. -COOH, -SO3H, -PO3H2, -OSO3H, -OPO2H2; Salts thereof

Definitions

  • a photo graphic silver halide emulsion layer usually a gelatino silver halide emulsion layer, includes as a uniform dispersion therein, a suitable dyestufi.
  • the layer is exposed to light or otherwise rendered developable so that a latent silver image is formed therein. This image 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 (or bleaching) the dyestuff in the region of the silver image.
  • the silver salts and any residual silver are then removed from the layer and the layer then contains only a dyestufi image which is complementary in sign to the original silver image.
  • the layer may be dyed with the dyestuff after the exposure step or after the development of the silver image.
  • the dyestulf 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 others sensitised to green and red light respectively.
  • a blue-absorbing filter layer between these latter layers and the emulsion which is sensitive only to blue, a common form of assembly being:
  • Polychromatic light incident on layer (e) causes the formation of latent silver images in layers (e), (e) 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 (0) 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.
  • One of the principal difiiculties in the silver-dye-bleach process is the selection of suitable dyestuffs for the purpose. Some hundreds of dyestuffs have been suggested, but most of the dyestufifs proposed are unsatisfactory in one or more respects.
  • a principal difiiculty is to ensure that the dyestufi employed will not difliuse from the gelatin emulsion layer in which it is incorporated, and various proposals, such as mordanting, have been made to overcome this dilficulty.
  • dyestuffs for use, moreover, it is desirable that they should be bleached rapidly by the bleaching baths employed and also preferable that their inclusion in the emulsion layer should not too seriously reduce the sensitivity of the emulsion.
  • the dye should approach as closely as possible to the theoretical requirement that, of red, blue and green light it should absorb all of one while fully transmitting or reflecting both of the others.
  • the present invention is concerned with the provision of a new class of cyan dyestuffs for use in the silver-dyebleach process, which approach more closely to the desiderata set forth above.
  • a process for the production of a cyan dyestuff image in a photographic layer comprises including in a light-sensitive gelatino silver halide emulsion layer, or in a plain gelatin layer coated adjacent thereto, a cyan dyestufi of the formula:
  • sons diazotising the product and coupling it with a compound of the formula:
  • a process of colour photography comprises a process as just set forth in which the said gelatino-silver-halide layer is sensitive to red light and constitutes one of the layers of a multilayer photographic material which further contains photographic emulsion layers sensitive to blue and green light respectively dyed with yellow and magenta dyestuffs, and the said cyan dyestuff is included in the said 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:
  • 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 dyestufi as above set forth.
  • Preferred dyestuffs within the general formula given above are those in which R is a methyl or ethyl group and the sulphonic acid of the middle naphthalene ring is in the 6 or 7 (preferably the 6) position.
  • One of the sulphonic acid groups in the right-hand naphthalene nucleus is preferably in the 4 or 6 position of that nucleus with respect to the 8-hydroxyl group and where a second sulphonic acid group is present it is preferably in the 2, 3 or 4 position depending on the position of the first sulphonic acid group.
  • Preferred positions where two sulphonic acid groups are present are the 3:6 and 2:4 positions.
  • the bleaching of the cyan dyestuffs employed in this invention can be effected by any of the types of bleaching bath commonly employed in the silver-dye-bleach process.
  • the pale yellowish coloured, clear diazo solution is poured within 2 hours into a suspension of 25.3 parts of 1-amino-2-methoxynaphthalene6-su1- phonic acid and 60 parts of sodium acetate in 500 parts of water and 500 parts of ice. This is performed at 0-5. The coupling occurs immediately and the colour changes to red. The whole is stirred for 6 hours at this temperature, the acid is then neutralised by the gradual addition of 32 parts of sodium carbonate and the precipitated dyestuif is filtered off under suction. It is washed in the suction filter with a 5% sodium chloride solution.
  • the brownish-red monazo dyestuff is dissolved at the boil in 4000 parts of hot water in the presence of 2 g. per litre of the condensation product of dodecyl alcohol and 20 mol of ethylene oxide as dispersing agent, 6.9 parts of sodium nitrite are added, the reaction mixture is cooled to 25 and 40 parts of concentrated hydrochloric acid are added. After stirring for 15 hours at 25-30" a little excess nitrous acid is decomposed with sulphamic acid.
  • the brown-yellowish gelatinous diazo emulsion is then poured at 15-20 into a solution of 36.1 parts of 1-acetylamino-8-hydroxynaphthalene-3.-disulphonic acid and parts of sodium acetate in 1000' parts of water and 250 parts of pyridine.
  • the coupling takes place immediately and the colour changes to cyan.
  • Stirring is continued for 4 hours at the same temperature, 600 parts of potassium chloride are added and the dyestuif which precipitates is filtered off under suction. It is washed first with 500 parts of a solution consisting of 50 parts of pyridine, 25 parts of potassium chloride and 350 parts of water, then with 500 parts of pyridine and, finally, with 200 parts of acetone, after which it is dried at 80.
  • the dyestuif is a blue powder which dissolves in Water with a cyan colouration and in concentrated sulphuric acid with a blue colouration.
  • the 3-amino-4-phenoxybenzene-l-carboxylic acid decyl ester used as starting component is obtained by condensing 4-chloro-3-nitrobenzene-l-carboxylic acid with excess phenol in the presence of 2.2 mols of potassium hydroxide at temperatures of over C., isolating the free 4-phenoxy-3-nitrobenzene-l-carboxylic acid, converting this with thionyl chloride into carboxylic acid chloride, reacting the chlorid with n-decyl alcohol to form the decyl ester and finally reducing the nitro group to the amino group in aqueous ethyl alcohol.
  • the following table contains some further disazo dyestuffs which can be used and which can be produced by the method described above. If the starting components are homologous and isomeric or analogous compounds, they are also obtained by the method described above.
  • the dyestuli is a blue powder which dissolves in water added, the dyestufi suspension is heated to 40 C. The With a cyan colouration and in concentrated sulphuric acid precipitated blue disazo dyestulf is filtered off under sucwith a blue colouration.
  • monoazo dyestuff is dissolved in 4000 parts of boiling
  • the dyestufl is a blue powder which dissolves in water water, 6.9 parts of sodium nitrite are added, the tem- With a cyan colouration and in concentrated sulphuric perature is reduced to 25C. and parts of concentrated acid with a deep blue colouration. 40 hydrochloric acid are added. After stirring for 20 hours DYESTUFF NO. 3
  • the dyestuft' is a blue powder which dissolves in water added, the solution is cooled to 25 C. and 40 parts of conwith a cyan colouration and in concentrated sulphuric centrated hydrochloric acid are added. After stirring for acid with a dark blue co louration,
  • the dried coating is exposed to light to record an image therein and processed at 6 8 F. as follows:
  • Steps 4 and 5 may be omitted if the original emulsion is hardened or provided with a hardened gelatin supercoat.
  • a light-sensitive gelatino silver halide emulsion comprising a cyan dyestuif of the formula:
  • A is a radical selected from the class consisting of phenyland phenoxyphenyl-carboxylic alkyl esters of which the alkyl group contains at least 5 carbon atoms
  • R is selected from the class consisting of alkyl groups containing up to 6 carbon atoms and carboxymethyl groups
  • X is selected from the class consisting of hydroxy, amino, alkyl carbonylamino, phenylalkyl carbonylamido, phenyl carbonylamido, haloalkyl carbonylamido, halophenyl-alkyl carbonylamido, halophenyl carbonylamido and halophenoXy-alkyl carbonylamido groups
  • n is an integer at least 1 and not more than 2.
  • a multilayer photographic material comprising a layer of gelatino silver halide emulsion containing a cyan dye and sensitive to red light, a layer of gelatino silver halide emulsion containing a yellow dye and sensitive to blue light, and a layer of a gelatino silver halide emulsion containing a magenta dye and sensitive to green light, wherein the cyan dye is of the formula:
  • A is a radical selected from the class consisting of phenyland phenoxyphenyl-carboxylic alkyl esters of which the alkyl group contains at least 5 carbon atoms
  • R is selected from the class consisting of alkyl groups containing up to 6 carbon atoms and carboxymethyl groups
  • X is selected from the class consisting of hydroxy, amino, alkyl carbonylamido, phenylalkyl carbonylamido, phenyl carbonylamido, haloal kyl carbonylamido, halophenyl-alkyl carbonylamido, halophenyl carbonylamido and halophenoXy-alkyl carbonylamido groups
  • n is an integer at least 1 and not more than 2.
  • a multilayer photographic material comprising an assembly consisting of:
  • A is a radical selected from the class consisting of phenyland phenoxyphenyl-carboxylic alkyl esters of which the alkyl group contains at least 5 carbon atoms
  • R is selected from the class consisting of alkyl groups containing up to 6 carbon atoms and carboxymethyl groups
  • X is selected from the class consisting of hydroxy, amino, alkyl carbonyl amido, phenylalkyl carbonylamido, phenyl carbonylamido, haloalkyl carbonylamido, halophenylalkyl carbonylamido, halophenyl carbonylamido and halophenoxy-alkyl carbonylamido groups
  • n is an integer at least 1 and not more than 2.
  • cyan dyestuff is:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US800639A 1957-04-29 1959-03-20 Photographic color element with novel cyan dye Expired - Lifetime US3038802A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE567189D BE567189A (sr) 1957-04-29
US728065A US3002964A (en) 1957-04-29 1958-04-14 Colour photography
FR1205587D FR1205587A (fr) 1957-04-29 1958-04-28 Photographie en couleurs
DEG24411A DE1077531B (de) 1957-04-29 1958-04-28 Verfahren zur Erzeugung eines blaugruenen Farbstoffbildes in einer photographischen Schicht
US800639A US3038802A (en) 1957-04-29 1959-03-20 Photographic color element with novel cyan dye

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB1359857A GB847527A (en) 1957-04-29 1957-04-29 Improvements in or relating to colour photography
US728065A US3002964A (en) 1957-04-29 1958-04-14 Colour photography
US800639A US3038802A (en) 1957-04-29 1959-03-20 Photographic color element with novel cyan dye

Publications (1)

Publication Number Publication Date
US3038802A true US3038802A (en) 1962-06-12

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US800639A Expired - Lifetime US3038802A (en) 1957-04-29 1959-03-20 Photographic color element with novel cyan dye

Country Status (4)

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US (1) US3038802A (sr)
BE (1) BE567189A (sr)
DE (1) DE1077531B (sr)
FR (1) FR1205587A (sr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3114634A (en) * 1960-10-27 1963-12-17 Ilford Ltd Colour photography
US3178290A (en) * 1960-07-06 1965-04-13 Ciba Ltd Photographic layers suitable for the silver dyestuff bleaching method
US3287132A (en) * 1962-09-24 1966-11-22 Ilford Ltd Silver dye bleach dyestuffs and their use in colour photography
US3436218A (en) * 1959-06-12 1969-04-01 Ciba Geigy Corp Process for producing color photographs
US9700196B2 (en) 2011-05-16 2017-07-11 Whirlpool Corporation Dishwasher with filter assembly

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB298979A (en) * 1927-10-18 1930-02-20 Friedrich Lierg Process of producing pictures consisting of dyes in photographic manner
US1880572A (en) * 1929-09-09 1932-10-04 Agfa Ansco Corp Color photography
US2694636A (en) * 1951-08-16 1954-11-16 Geigy Ag J R Light-sensitive element for color photography

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL88079C (sr) * 1951-07-31

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB298979A (en) * 1927-10-18 1930-02-20 Friedrich Lierg Process of producing pictures consisting of dyes in photographic manner
US1880572A (en) * 1929-09-09 1932-10-04 Agfa Ansco Corp Color photography
US2694636A (en) * 1951-08-16 1954-11-16 Geigy Ag J R Light-sensitive element for color photography

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3436218A (en) * 1959-06-12 1969-04-01 Ciba Geigy Corp Process for producing color photographs
US3178290A (en) * 1960-07-06 1965-04-13 Ciba Ltd Photographic layers suitable for the silver dyestuff bleaching method
US3114634A (en) * 1960-10-27 1963-12-17 Ilford Ltd Colour photography
US3287132A (en) * 1962-09-24 1966-11-22 Ilford Ltd Silver dye bleach dyestuffs and their use in colour photography
US9700196B2 (en) 2011-05-16 2017-07-11 Whirlpool Corporation Dishwasher with filter assembly

Also Published As

Publication number Publication date
FR1205587A (fr) 1960-02-03
DE1077531C2 (sr) 1960-09-01
BE567189A (sr)
DE1077531B (de) 1960-03-10

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