EP0182658B1 - Photographische Kupplerdispersionen - Google Patents

Photographische Kupplerdispersionen Download PDF

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Publication number
EP0182658B1
EP0182658B1 EP19850308436 EP85308436A EP0182658B1 EP 0182658 B1 EP0182658 B1 EP 0182658B1 EP 19850308436 EP19850308436 EP 19850308436 EP 85308436 A EP85308436 A EP 85308436A EP 0182658 B1 EP0182658 B1 EP 0182658B1
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EP
European Patent Office
Prior art keywords
coupler
anionic surfactant
photographic
dispersion
lipophilic
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
Application number
EP19850308436
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English (en)
French (fr)
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EP0182658A3 (en
EP0182658A2 (de
Inventor
Michael J. Dr. Simons
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.)
Kodak Ltd
Eastman Kodak Co
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Kodak Ltd
Eastman Kodak Co
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Publication of EP0182658A2 publication Critical patent/EP0182658A2/de
Publication of EP0182658A3 publication Critical patent/EP0182658A3/en
Application granted granted Critical
Publication of EP0182658B1 publication Critical patent/EP0182658B1/de
Expired legal-status Critical Current

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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
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3885—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific solvent

Definitions

  • This invention relates to dispersions of couplers useful in the manufacture of sensitive silver halide colour photographic materials.
  • a common method of preventing coupler diffusion comprises providing the coupler with a water-insoluble 'ballast' group and, before mixing it with the relevant coating composition, dispersing it as a uniform mixture with a water-insoluble high-boiling organic solvent, termed a coupler solvent or an 'oil-former', on an aqueous gelatin solution.
  • a surface-active agent is used to facilitate the dispersion process and to help stabilise the dispersion obtained.
  • Many photographic coupler dispersions contain compounds with phenolic or naphtholic groups of which the acidity is enhanced by the presence of electron-withdrawing substituents in the ortho and/or para positions relative to the hydroxyl group.
  • Well-known compounds of this kind are certain phenolic and naphtholic cyan dye-forming couplers, but couplers for producing dyes of other colours are known which contain such acidic groups. It has been found that the dark stability of dyes formed by colour development of photographic materials containing dispersions of phenolic or naphtholic compounds with enhanced acidity is not as good as is desirable.
  • the present invention is based upon the discovery that the adverse affect on dye stability of the phenolic or naphtholic compound can be mitigated to a useful extent by use of certain lipophilic anionic surfactants in preparing the relevant dispersions. Additional anionic surfactants of more conventional type may be used to aid the dispersion process but non-ionic surfactants have been found to reduce the beneficial effect of the lipophilic surfactant and so are excluded.
  • a method of making a photographic coupler dispersion by dispersing a mixture containing the coupler and an oil-former in an aqueous hydrophilic colloid solution in the presence of an anionic surfactant, the coupler and/or the oil-former comprising a phenolic or naphtholic moiety of which the acidity is enhanced by the presence of at least one electron-withdrawing group at a position ortho or para to the phenolic hydroxyl group, wherein there is added at any stage an anionic surfactant which may be said anionic surfactant above which comprises a sulphate or sulphonate group as the sole hydrophilic group and either a single aliphatic hydrocarbon group having at least 15 carbon atoms or two or more aliphatic hydrocarbon groups which together contain at least 17 carbon atoms, but wherein no non-ionic surfactant is used.
  • anionic surfactant defined above is referred to below simply as the lipophilic anionic surfactant.
  • the coupler dispersions contain in the oily, dispersed, phase, at least one compound comprising a phenolic or naphtholic moiety, each such compound having at least one electron-withdrawing substituent in a position ortho or para to the phenolic hydroxyl group which enhances the acidity of that group.
  • R is an alkyl or aryl group
  • each of R 1 and R 2 is hydrogen or an alkyl or aryl group
  • R 3 is an aryl or heterocyclic group
  • M is a cation, any group R, R', R 2 and R 3 possibly being itself substituted with such substituents as alkyl, alkoxy, aryl, aryloxy, halogen, nitro, and carboxylic acid, ester and amide groups.
  • a suitable substituent for the phenolic or naphthoic moiety has a Hammett p-Substituent Constant greater than zero: See, for instance, the article by Exner in the book'Advances in Linear Free Energy Relationships', edited by Chapman and Shorter, Plenum Press (London) 1972.
  • the compound comprising the acidic phenolic, or naphtholic, moiety may be the coupler itself, in which case it may be a suitably substituted member of one of the various classes of cyan dye-forming coupler.
  • couplers are described in, for example:
  • the compound comprising the acidic phenolic or naphtholic moiety may be a coupler giving, on colour development, a magenta or yellow dye, coupling taking place preferentially at a pyrazolone or active methylene coupling position rather than at a position para to the hydroxyl group of the phenolic or naphtholic moiety.
  • Couplers of this kind are described in, for instance: U.K. Patent Specification 1,474,128.
  • Coupler solvents having acidic phenolic or naphtholic moieties are described in, for instance: US Patent 4,207,393 and 4,228,235.
  • Coupler solvents Any of the usual coupler solvents may be employed as the oil-former in a dispersion of the invention. Suitable solvents are inert high-boiling liquids or low-melting solids, well-known examples being dibutyl phthalate and tricresyl phosphate. Numerous other coupler solvents are described in UK Patent Specification 541,589.
  • a coupler dispersion contains an anionic surfactant which comprises, as the sole hydrophilic group, a group of formula -S0 3 M or -OS0 3 M (where M is any convenient cation) and either a single aliphatic hydrocarbon group having at least 15 carbon atoms or two or more aliphatic hydrocarbon groups which together contain at least 17 carbon atoms.
  • the aliphatic hydrocarbon group or groups may contain unsaturation and the surfactant molecule may contain such non-hydrophilic features as ether, amide or sulphonamide linkages and ester groups.
  • Classes of surfactant having at least some members in accordance with these requirements include:
  • Preferred surfactants from these classes are alkane sulphonates (class i) of formula: R'S0 3 M and alkylphenol sulphonates (class ix) of formula: wherein R 1 is a straight chain alkyl or alkenyl group of at least 15 carbon atoms, and M is a cation, and dialkylsulphosuccinates (class xi) of formula: wherein m+n is at least 17, m and n being the same or different, M in the above formulae is a hydrogen ion, an alkali metal ion or any other suitable cation.
  • a mixture of two or more compounds may be used.
  • two or more couplers, coupler solvents or lipophilic surfactants may be employed, it being necessary for only one of these compounds to comprise an acidic phenolic or naphtholic moiety.
  • the dispersing agent used in a method of the invention may also include an additional, and less lipophilic, anionic surfactant.
  • an additional, and less lipophilic, anionic surfactant This may be from the classes (i) to (xiii) listed above, the reduced lipophilic character being achieved through the presence of fewer carbon atoms in the aliphatic hydrocarbon group or groups present or through the presence of more than one hydrophilic group, any additional group being, for instance an hydroxyl, or a carboxylic acid or salt, group.
  • a second anionic surfactant may contain a single group -S0 3 M or -OS0 3 M and either a single aliphatic hydrocarbon group having fewer than 15 carbon atoms or two or more aliphatic hydrocarbon groups which together contain fewer than 17 carbon atoms.
  • an additional anionic surfactant may be of some other class such as a sulphonated monoglyceride, a sulphated fat or oil having a free carboxyl group, and a-sulphocarboxylic acid, an alkyl glyceryl ether sulphonate or an N-acylated-amino acid.
  • the coupler-coupler solvent solution or mixture is dispersed, with the aid of a surfactant or surfactant mixture, in an aqueous hydrophilic colloid solution.
  • the colloid is preferably gelatin or a simple derivative such as phthalated gelatin.
  • the dispersion step in a method of the invention may be effected conventionally using any high-speed mixing device.
  • a water-miscible or volatile water-immiscible 'auxiliary solvent' may be present, being removed by washing with water from the set dispersion or when volatile, by evaporation under reduced pressure.
  • Auxiliary solvents and their use are described in, for example, U.S. Patent 2,801,171.
  • the compound comprising a phenolic or naphtholic moiety of enhanced acidity, or mixture of such compounds preferably constitutes at least 5% by weight of an oil phase (i.e. the coupler, water-immiscible solvent and lipophilic anionic surfactant) and the lipophilic anionic surfactant preferably constitutes at least 1 % by weight of the oil phase.
  • an oil phase i.e. the coupler, water-immiscible solvent and lipophilic anionic surfactant
  • the lipophilic anionic surfactant preferably constitutes at least 1 % by weight of the oil phase.
  • the weight of lipophilic surfacent is usually present at a concentration of from 1 to 100% by weight, the preferred range being 3 to 20%.
  • a coupler dispersion made by a method of the invention is employed conventionally in the manufacture of incorporated-coupler silver halidecolour photographic materials, both negative and positive.
  • Numerous references to patent specifications and other publications relating to silver halide photographic materials, including colour materials and their processing, are given in Research Disclosure December 1978, Item 17643 (see especially sections VII, XI, XIV and XIX).
  • the dispersion is mixed with the appropriate coating composition, usually a gelatino-silver halide photographic emulsion, prior to coating.
  • Photographic coatings were prepared by combining together, under safelight conditions, 1.5 g of coupler dispersion, 1.5 g of 12./2% w/v aqueous gelatin solution, 0.20 ml of photographic paper type silver chlorobromide emulsion (approximately 1.0 molar in silver halide) and 5.5 ml water. 5% w/v chromic sulphate solution, 0.30 ml, was added immediately prior to coating on photographic film base at a wet thickness of approximately 0.1 mm.
  • Portions of dried coating were exposed to room light for 5s and then developed for 210 s in a p-phenylenediamine developer (KODAK 'Ektaprint 2', trade mark) at 31 °C, bleach-fixed for 120s in a bleach-fix solution (KODAK 'Ektaprint'), washed for 30 minutes in running water, and dried.
  • a p-phenylenediamine developer (KODAK 'Ektaprint 2', trade mark) at 31 °C
  • bleach-fixed for 120s in a bleach-fix solution (KODAK 'Ektaprint')
  • the resulting cyan density of each sample was measured with a transmission densitometer through a red filter.
  • the samples were then incubated in an oven at 60°C and 70% relative humidity and the dye density measured from time to time.
  • the initial optical density (D,) and the percentage density loss at the various times are reorded in Table 1.
  • This example illustrates the use of a combination of hydrophilic and hydrophobic surfactants.
  • a coupler dispersion was prepared by dissolving coupler 1, 5.0 g, in di-n-butyl phthalate, 2.8 g together with 2-(2-butoxyethoxy) ethyl acetate, 0.4 g, and mechanically dispersing the resulting oily solution in 11.5% w/v gelating solution, 42 g, containing sodium tri-isopropylnaphthalene sulphonate, 0.18 g. Portions of 10 g were withdrawn, and 10% w/v solutions of sodium bis (tridecyl) sulphosuccinate in 1:2 methanol:water were added as in Table 2 and mechanically dispersed into the dispersion.
  • Photographic coatings were prepared by combining together, under safelight conditions, 1.0 g of coupler dispersion, 1.5 g of 12.1/2% w/v aqueous gelatin solution, 0.20 ml of photographic paper type silver chlorobromide emulsion (approximately 1.0 molar in silver halide), and 6.0 ml water. 5% w/v chromic sulphate solution, 0.30 ml, was added immediately prior to coating on photographic film base at a wet thickness of approximately 0.1 mm.
  • Example 2 Portions of dried coatings were exposed, processed and tested as in Example 1: the results are given in Table 2.
  • a low humidity accelerated keeping test was also carried out by placing processed strips in an oven at 77°C with no added humidity, and measuring the dye density at intervals as before. These results are given in Table 3.
  • This example illustrates another combination of hydrophilic and hydrophobic surfactants.
  • Coupler dispersions were prepared by dissolving together 1.0 g of coupler I, 0.6 g of tricresyl phosphate, and 0.10 g of sodium bis (tridecyl) sulphosuccinate, and mechanically dispersing the resulting oily solution into 5.0 g of a 12.1/2% w/v aqueous gelatin solution mixed with 3.0 ml water and 10% w/v aqueous sodium dioctyl sulphosuccinate (a non-lipophilic anionic surfactant) as stated in Table 4.
  • the dispersion prepared for Example 2 was used for the control.
  • Example 2 Coatings were prepared as in Example 2, except that 0.9 ml of dispersion and 6.1 ml of water were added. Testing was as in Example 2, and results are given in Tables 4 and 5.
  • the washed dispersion was melted at 40°C and to a 5.0 g portion was added 0.2 g of a 70% w/w solution of sodium bis (tridecyl) sulphosuccinate ('Aerosol TR70' - trade mark - supplied by Cyanamid of Great Britain Limited). This solution was mechanically dispersed into the dispersion sample.
  • Coatings were prepared as in Example 2, except that 1.3 g of dispersion and 4.9 ml of water were used for each coating. Testing was carried out as in Example 2 and the results are as shown in Table 6.
  • Dispersions of coupler were prepared by dissolving coupler, 1.5 g, in di-n-butyl phthalate, 0.9 gl and ethyl acetate, 0.9 g, and mechanically dispersing the resultant solution in 15 g of 9.2% w/w gelatin to which had been added 10% sodium triisopropyl naphthalene sulphonate, 0.6 ml.
  • Photographic coatings were prepared by combining together, under safelight conditions, the treated portion of coupler dispersion, 1.5 g of 12 1/2 w/v aqueous gelatin solution, 0.25 ml of photographic paper type silver chlorobromide emulsion (approximately 1.0 molar in silver halide) and 5.7 ml of water.
  • Couplers III to V had the structures:
  • This Example illustrates the use of the surfactants when coupler IV was dispersed in the presence of an acidic phenol coupler solvent.
  • Coupler IV 1.0 g; n-dodecyl-p-hydroxybenzoate, 0.33 g; n-octyl-p-hydroxy-benzoate, 0.33 g; and N,N-diethyl lauramide, 0.33 g, were melted together to form an oily solution.
  • This solution was mechanically dispersed into 7.6 g of 10.5% w/w gelatin solution, to which had been added 0.8 g of 10% w/w sodium dioctyl sulphosuccinate aqueous solution and other surfactants as stated in Table 9
  • Photographic coatings were prepared by combining together under safelight conditions, 0.8 g of coupler dispersion, 0.25 g of silver chlorobromide photographic paper emulsion (approximately 1.0 molar in silver halide), 1.0 g of 12% w/w gelatin aqueous solution, and 6.6 ml of water. 5% w/v chromic sulphate solution, 0.30 ml, was added immediately prior to coating on photographic film base at a wet thickness of approximately 0.10 mm.
  • the coupler used in this Example had an acidic phenol leaving group.
  • the results show how the dark stability of the image dye was most diminished in areas of low image density, where most acidic phenol remained.
  • the stabilising effect of the surfactants is illustrated; the effects varied with the humidity at which the accelerated dark fading was carried out.
  • a coupler dispersion and coatings were prepared as in Example 5, except that coupler VI was used.
  • the coatings were exposed to a photographic step wedge and processed as in Example 5.
  • the image densities of the various steps of the image were measured (blue filter).
  • the strips were incubated either for 60 days at 60°C, 70% RH or for 28 days at 77°C. low RH. Results are given in Table 10: coating A had 0.3 ml water added, B had 0.3 ml 7% Aerosol TR70, as in Example 5.
  • Multilayer coatings were made on a paper support according to the following.summary.
  • the numbers in parenthesis are coverages expressed as mg/m 2.
  • the coverages relate to the silver present.
  • Couplers were incorporated in the layers as dispersions, being mixed with di-n-butyl phthalate (one half the coupler weight in the case of the cyan and magenta couplers and one quarter the coupler weight in the case of the yellow coupler) and dispersed in aqueous gelatin solutions with the aid of sodium tri- ispropyl naphthalene sulphonate.
  • the UV absorber in layer 4 comprised a mixture of 84.1 % (by weight) of 2-(2-hydroxy-3,5-di-tert-pentyl-phenyl) benzotriazole, 15% 2-(2-hydroxy-3-tert-butyl-5-methylphenyl) benzotriazole and 0.9% dioctylhydroquinone dispersed in 2-(2-butoxyethoxy) ethyl acetate.
  • the gelatin hardener in layer 1 was bis(vinylsulphonylmethyl) ether and was added in an amount equal to 1.75% of the total weight of the gelatin in the multilayer coating.
  • Samples of the four coatings were exposed, processed as described in Example 1 and then used for determining the stability of the cyan dye image under incubation test conditions. In all the tests the loss in red-light reflection density of an image having an initial value of 1.7 was measured as a function of the incubation time. Two different test conditions were used, 77°C and 15% relative humidity for the two week tests and 60°C and 70% relative humidity for 16 week tests.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (11)

1. Verfahren zur Herstellung einer photographischen Kupplerdispersion durch Disperigieren einer Mischung, die den Kuppler und einen Öl-Bildner enthält, in einer wäßrigen, hydrophilen Kolloidlösung in Gegenwart eines anionischen oberflächenaktiven Mittels, wobei der Kuppler und/oder der Öl-Bildner einen phenolischen oder naphtholischen Rest aufweisen, dessen Acidität durch die Gegenwart von mindestens einer Elektronen abziehenden Gruppe in einer Position ortho oder para zur phenolischen Hydroxylgruppe gesteigert wird, in dem zu irgendeinem Zeitpunkt ein anionisches oberflächenaktiven Mittel zugesetzt wird, das das oben erwähnte anionische oberflächenaktive Mittel sein kann und das eine Sulphat- oder Sulphonatgruppe als einzige hydrophile Gruppe un entweder 'eine einzelne aliphatische Kohlenwasserstoffgruppe mit mindestens 15 Kohlenstoffatomen oder zwei oder mehr aliphatischen Kohlenwasserstoffgruppen, die zusammen mindestens 17 Kohlenstoffatome enthalten, aufweist (im folgenden als lipophiles anionisches oberflächenaktives Mittel bezeichnet) und bei dem jedoch kein nichtionisches oberflächenaktives Mittel verwendet wird.
2. Verfahren nach Anspruch 1, in dem das lipophile anionische oberflächenaktive Mittel ein Alkylphenolsulphonat oder ein Dialkylsulphosuccinat ist.
3. Verfahren nach einem der vorstehenden Ansprüche, in dem das anionische oberflächenaktive Mittel, das während der Dispersionstufe zugegen ist, ein oberflächenaktives Mittel umfaßt, das weniger lipophil ist als das angegebene lipophile anionische oberflächenaktive Mittel.
4. Verfahren nach einem der vorstehenden Ansprüche, in dem das lipophile anionische Mittel vor der Dispersionsstufe zugesetzt wird.
5. Verfahren nach einem der vorstehenden Ansprüche, in dem der Kuppler ein phenolischer oder naphtholischer, einen blaugrünen Farbstoff bildender Kuppler ist.
6. Verfahren nach einem der vorstehenden Ansprüche, in dem das Kupplerlösungsmittel eine phenolische oder naphtholische Gruppe von erhöhter Acidität aufweist.
7. Verfahren nach einem der vorstehenden Ansprüche, in dem die Verbindung mit einer phenolischen oder naphtholischen Gruppe von erhöhter Acidität oder Mischungen solcher Verbindungen, mindestens 5 Gew.-% der dispergierten Substanzen ausmacht, bzw. ausmachen.
8. Verfahren nach einem der vorstehenden Ansprüche, in dem die Gesamtmenge an lipophilem oberflächenaktiven Mittel mindestens 1 Gew.-% der dispergierten Substanzen ausmacht.
9. Empflindliches photographisches Material mit einem Träger, der eine photographische hydrophile Kolloid-Silberhalogenidemulsionsschicht aufweist und dispergiert in der Schicht oder einer hierzu benachbarten hydrophilen Kolloidschicht, eine photographische Kupplerdispersion, die nach einem der Ansprüche 1 bis 8 hergestellt wurde.
10. Material nach Anspruch 9, in dem die photographische Kupplerdispersion ein Alkansulphonat, ein Alkylphenylsulphonat oder ein Dialkylsulphosuccinat aufweist.
11. Material nach Anspruch 9 oder 10, in dem die photographische Kupplerdispersion zusätzlich ein anionisches oberflächenaktives Mittel enthält, das eine aliphatische Kohlenwasserstoffgruppe mit weniger als 15 Kohlenstoffatomen oder zwei oder mehr aliphatische Kohlenwasserstoffgruppen mit zusammen weniger als 17 Kohlenstoffatomen aufweist.
EP19850308436 1984-11-23 1985-11-20 Photographische Kupplerdispersionen Expired EP0182658B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB848429677A GB8429677D0 (en) 1984-11-23 1984-11-23 Photographic coupler dispersions
GB8429677 1984-11-23

Publications (3)

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EP0182658A2 EP0182658A2 (de) 1986-05-28
EP0182658A3 EP0182658A3 (en) 1988-01-13
EP0182658B1 true EP0182658B1 (de) 1990-04-25

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EP19850308436 Expired EP0182658B1 (de) 1984-11-23 1985-11-20 Photographische Kupplerdispersionen

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EP (1) EP0182658B1 (de)
JP (1) JPS61184542A (de)
CA (1) CA1261190A (de)
DE (1) DE3577358D1 (de)
GB (1) GB8429677D0 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07119947B2 (ja) * 1986-09-11 1995-12-20 コニカ株式会社 新規な界面活性剤を含有するハロゲン化銀写真感光材料
US4933270A (en) * 1988-09-26 1990-06-12 Eastman Kodak Company Process for the precipitation of stable colloidal dispersions of base degradable components of photographic systems in the absence of polymeric steric stabilizers
US5015564A (en) * 1988-12-23 1991-05-14 Eastman Kodak Company Stabilizatin of precipitated dispersions of hydrophobic couplers, surfactants and polymers
US5089380A (en) * 1989-10-02 1992-02-18 Eastman Kodak Company Methods of preparation of precipitated coupler dispersions with increased photographic activity
US5380628A (en) * 1991-07-29 1995-01-10 Eastman Kodak Company Method of preparing coupler dispersions
JP2005070286A (ja) 2003-08-22 2005-03-17 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JP2005275160A (ja) 2004-03-25 2005-10-06 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1193349A (en) * 1967-10-30 1970-05-28 Ilford Ltd Dispersing Colour Couplers
GB1346425A (en) * 1970-08-13 1974-02-13 Agfa Gevaert Method of incorporating photographic compounds into hydrophilic colloids
JPS5066230A (de) * 1973-10-12 1975-06-04
JPS525518A (en) * 1975-07-03 1977-01-17 Fuji Photo Film Co Ltd Photographic light sensitive material

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DE3577358D1 (de) 1990-05-31
JPS61184542A (ja) 1986-08-18
EP0182658A3 (en) 1988-01-13
CA1261190A (en) 1989-09-26
EP0182658A2 (de) 1986-05-28
GB8429677D0 (en) 1985-01-03

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