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US2872317A - Colour photographic images produced from indazolone colour couplers - Google Patents

Colour photographic images produced from indazolone colour couplers Download PDF

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Publication number
US2872317A
US2872317A US342747A US34274753A US2872317A US 2872317 A US2872317 A US 2872317A US 342747 A US342747 A US 342747A US 34274753 A US34274753 A US 34274753A US 2872317 A US2872317 A US 2872317A
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US
United States
Prior art keywords
indazolone
colour
couplers
photographic images
parts
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
US342747A
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English (en)
Inventor
Woolley John Mathers
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.)
Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Publication date
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Publication of US2872317A publication Critical patent/US2872317A/en
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Classifications

    • 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
    • G03C7/3231—Couplers containing an indazolone ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
    • C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
    • C07K5/06—Dipeptides
    • C07K5/06008—Dipeptides with the first amino acid being neutral
    • C07K5/06078—Dipeptides with the first amino acid being neutral and aromatic or cycloaliphatic

Definitions

  • the colour coupler used in the process of our invention may .be used in the developing solution or it may be included in a light-sensitive layer or in a non-light-sensirive layer adjacent to a sensitive layer or separated therefrom by a water-permeable colloid layer.
  • colour couplers in one or more light-sensitive gelatinosilver halide emulsion layers which form part of a multilayer film or paper of the kind used for colour photography.
  • colour couplers which contain a substituent rendering them fast 5, to diffusion, for example an alkyl chain of at least 5 carbon atoms and, if desired, a solubilising group.
  • the colour couplers used in the process of our invention may be made by the general processes known for use in the synthesis of substituted indazolones or by treating the appropriate indazolone by processes known for replacing a hydrogen atom attached to a nitrogen atom by the radicals indicated by Y in the above formula.
  • the parent indazolone which may be substituted in the benzene nucleus may for example be made by causing a molecule of water to split off from the appropriate o-hydrazino-benzoic acid, for example by heating the latter in dilute hydrochloric acid, and the hydrogen atom attached to nitrogen in the 2-position can then be substituted.
  • Y is --COR, COOR, SO R,
  • CONHR, CONRR' or CSNHR in the above for mula the colour couplers may be made by treating the appropriate indazolone in boiling toluene with the appropriate acid chloride, chloroformic ester, sulphonyl chloride, isocyanate, di-N-substituted carbamyl chloride or isothiocyanate respectively.
  • the colour couplers used in the process of our invention have advantages over the known indazolone colour couplers which contain no substituent in the 2-position in that they are more resistant to oxidising agents and they do not give yellow oxidation products in the bleaching bath used for removal of silver.
  • Suitable colour couplers are 2- carbethoxy-indazolone, Z-phenylcarbamyl-indazolone, 2- naphthylcarbamyl-indazolone, Z-phenylthiocarbamyl-indazolone, Z-stearoyl-indazolone, 2-(p-toluene-sulphonyl)- indazolone and Z-phenylethyl carbamyl-indazolone.
  • Other specific compounds are mentioned in the examples below.
  • the aromatic amino compounds which may be used as developing agents in the present invention include the mono-, diand tri-amino-aryl compounds.
  • mono-amino developing agents may be mentioned aminophenols and amino-cresols and their halogen derivatives and amino-naphthols.
  • the developing agents preferably used and giving the best results in connection with the present invention are the aromatic orthoand para-diamines such as paraphenylene diamine and its substitution products.
  • the colour coupling which occurs in the process of our invention when an exposed gelatino-silver halide emulsion is treated with a primary aromatic amino developing agent in the presence of an indazolone substituted in the 2-position, proceeds by a surprising and wholly unexpected reaction in which the indazolone ring is split and an azo dyestufr' is formed in which the residue of the oxidation product of the developing agent is attached to the nitrogen atom which previously formed the l-nitrogen atom of the indazolone ring.
  • a dyestuff is formed which is believed to have the following formula:
  • a colour photographic element which contains in at least one emulsion layer a colour image comprising a dyestufr of the formula:
  • the dyestuff images formed by the process of our invention are superior to the known azamethine images in their chemical stability and their fastness to light and the process of our invention provides a simple method of obtaining colour photographic images of good fastness properties by direct development of an exposed gelatinosilver halide emulsion with aromatic amine colour developers.
  • Example 1 Two solutions are prepared with the following compositions.
  • the Z-carbethoxy-indazolone used in the above example is prepared as follows:
  • Example 2 1 part of 2-phenylcarbamyl-indazolone is dissolved in 160 parts of methanol. parts of Solution B described in Example 1, 20 parts of sodium acetate and 100 parts of Solution A described in Example 1 are added. The mixture is stirred until complete solution is obtained. A light sensitive gelatino-silver halide emulsion layer mounted on a support is exposed to light and developed in the above solution. The film is bleached and fixed when an orange image having an absorption maximum at 484 m is obtained.
  • Z-u-naphthyIcarbamyl-indazolone can be used when an orange image is formed.
  • this Z-tx-naphthyl compound is used the sodium acetate can be omitted from the developing solution.
  • the Z-phenylcarbamyl-indazolone used in the above example can be prepared as follows:
  • the corresponding 2-a-naphthyl compound can be similarly prepared from a-naphthylisocyanate.
  • Example 3 In place of the 1 part of Z-phenylcarbamyl-indazolone used in Example 2, there may be used 1 part of 2-phenylthiocarbamyl-indazolone when an orange image is obtained.
  • 2-phenylthiocarbamyl-indazolone may be prepared as follows:
  • Example 4 In place of the 1 part of 2-phenylcarbamyl-indazolone used in Example 2 there may be used 1 part of 2-stearoylindazolone when an orange image is obtained.
  • Z-stearoylindazolone may be prepared as follows:
  • a mixture of 850 parts of stearic acid, 400 parts of indazolone, 137 parts of phosphorus trichloride and 10,000 parts of toluene is boiled under a reflux condenser for 1 hour.
  • the reaction mixture is allowed to settle and the hot supernatant liquid is decanted from the tar and allowed to cool.
  • the 2-stearoyl-indazolone which crystallises out is filtered 0E.
  • the product is recrystallised from ethyl acetate when it melts at 122 C.
  • Example 5 In place of the 1 part of Z-carbethoxy-indazolone used in Example 1, 1 part of 2-(3-sulphobenzoyl)-5-chloroindazolone may be used.
  • This colour former may be obtained by reacting 3-chlorosulphonyl-benzoic acid with chloroindazolone in boiling toluene.
  • Example 7 6.7 parts of indazolone are dissolved in 100 parts of dioxane and a solution of 18.5 parts of octadecyl chloroformate in 42 parts of chlorobenzene is added. The suspension so obtained is boiled under a reflux condenser until a clear solution is obtained and no further evolution of hydrogen chloride occurs. The mixture is cooled and the white solid in suspension is-filtered off and washed firstly with cold methanol and then with ether and finally dried.
  • the 2-carboctadecoxy indazolone so obtained is incorporated into a lightsensitive gelatino-silver halide emulsion and the emulsion is coated on a film base and dried;
  • the light-sensitive film so obtained is exposed to light and developed with 2-methyl-4-diethylamino-aniline.
  • the film is then bleached and fixed and an orange dyestufi image of maximum absorption 500 m is obtained.
  • 2-carboctadecoxy-5:7-dibromo-indazolone may be used when a redder dyestufi image with maximum absorption at 520 m, is obtained.
  • 2-carboctadecoxy-4- chloro-, 5-chloro-, 6-chloro-, 5-bromo-, 5:7-dichloro-, 5- nitro-, 6-nitro-, 5-methoxy-, 6-methoxyor S-phenoxy-indazolones (which like the 5:7-dibromo compound mentioned above may be made by the action of octadecyl chloroformate on the parent indazolones carrying appropriate substituents in the benzene ring, which themselves may be made by the action of a dehydrating acid on the appropriate o-hydrazino-benzoic acids), 2-carboctadecoxy- 5acetylamino-, or 6-acetylaminoindazolones (which may be made in a similar manner from the acetylaminoindazolones which themselves may be made by acetylating the aminoin
  • R and R each represent a member of the group consisting of hydrocarbon, a sulfo-substituted hydrocarbon radical and a heterocyclic radical.
  • a light sensitive gelatino silver halide emulsion layer according to claim 4 which contains a substituent rendering the colour coupler fast to difiusion and a solubilising group.
  • Z represents the non-metallic atoms required for completing an aromatic nucleus
  • Y represents a substituent from the group consisting of --COR, COOR, -SO R, CONHR, CONRR and CSNHR wherein R and R each represent a member of the group consisting of hydrocarbon, a sulfo-substituted hydrocarbon radical and a heterocyclic radical, said colour coupler containing a substituent rendering the colour coupler fast to diffusion and a solubilizing group.
  • the colour coupler is selected from the group consisting of unsubstituted and substituted indazolone compounds, wherein the substituent is designated by the letter R and is selected from the group consisting of a halo group, a hydrocarboxy group, a nitro group, an acylamino group and a hydrocarbonureido group attached to the benzene ring of the indazolone nucleus, said compound having the formula o l R El ⁇ NY wherein Y represents a substituent from the groupconsisting of COR, COOR, SO R, -CONHR, --CONRR', CSNHR, wherein R and R each represent a member of the group consisting of a hydrocarbon, a sulfo-substituted hydrocarbon radical and a heterocyclic radical.
  • the color coupler is an unsubstituted indazolone compound of the formula wherein Y represents a substituent from the group consisting of COR, COOR, -SO2R, CONHR,.
  • R and R each represent a member of the group consisting of a hydrocarbon, a sulfo-substituted hydrocarbon radical and a heterocyclic radical.
  • a process for the production of colored photographic images which comprises developing an exposed gelatinosilver halide emulsion layer by means of a primary aromatic amino developing agent in the presence of a color coupler of the formula:
  • Z represents the non-metallic atoms required for completing an aromatic nucleus
  • Y represents an acyl group

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Biophysics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Genetics & Genomics (AREA)
  • General Health & Medical Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Medicinal Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US342747A 1952-03-21 1953-03-16 Colour photographic images produced from indazolone colour couplers Expired - Lifetime US2872317A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB7338/52A GB722281A (en) 1952-03-21 1952-03-21 Colour photographic images

Publications (1)

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US2872317A true US2872317A (en) 1959-02-03

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US342747A Expired - Lifetime US2872317A (en) 1952-03-21 1953-03-16 Colour photographic images produced from indazolone colour couplers

Country Status (6)

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US (1) US2872317A (de)
BE (1) BE518561A (de)
CH (3) CH320355A (de)
DE (1) DE1009024B (de)
FR (1) FR1075746A (de)
GB (1) GB722281A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964402A (en) * 1951-10-03 1960-12-13 Gevaert Photo Prod Nv Mono-acetyl indazolone color couplers
US3171740A (en) * 1960-02-11 1965-03-02 Agfa Ag Process for the production of colored photographic non-transparent or transparent images
US4481268A (en) * 1981-02-09 1984-11-06 Eastman Kodak Company Method of forming a photographic dye image

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB663190A (en) * 1948-11-23 1951-12-19 Gevaert Photo Producten Naamlo Improvements in and relating to the production of colour photographic images
US2651638A (en) * 1953-09-08 Derivatives of i
US2655508A (en) * 1950-11-10 1953-10-13 Lilly Co Eli Pyrazole compound
US2672417A (en) * 1949-12-31 1954-03-16 Gevaert Photo Prod Nv Production of color photographic images

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE814196C (de) * 1948-10-02 1951-09-20 Telefunken Gmbh Einrichtung zum stellenweisen Auftauen des Erdbodens

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2651638A (en) * 1953-09-08 Derivatives of i
GB663190A (en) * 1948-11-23 1951-12-19 Gevaert Photo Producten Naamlo Improvements in and relating to the production of colour photographic images
US2673801A (en) * 1948-11-23 1954-03-30 Gevaert Photo Prod Nv Production of color photographic images
US2672417A (en) * 1949-12-31 1954-03-16 Gevaert Photo Prod Nv Production of color photographic images
US2655508A (en) * 1950-11-10 1953-10-13 Lilly Co Eli Pyrazole compound

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964402A (en) * 1951-10-03 1960-12-13 Gevaert Photo Prod Nv Mono-acetyl indazolone color couplers
US3171740A (en) * 1960-02-11 1965-03-02 Agfa Ag Process for the production of colored photographic non-transparent or transparent images
US4481268A (en) * 1981-02-09 1984-11-06 Eastman Kodak Company Method of forming a photographic dye image

Also Published As

Publication number Publication date
FR1075746A (fr) 1954-10-19
CH320355A (de) 1957-03-31
CH322538A (de) 1957-06-15
BE518561A (de)
CH322539A (de) 1957-06-15
GB722281A (en) 1955-01-19
DE1009024B (de) 1957-05-23

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