EP0777151B1 - Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process - Google Patents

Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process Download PDF

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Publication number
EP0777151B1
EP0777151B1 EP19960203192 EP96203192A EP0777151B1 EP 0777151 B1 EP0777151 B1 EP 0777151B1 EP 19960203192 EP19960203192 EP 19960203192 EP 96203192 A EP96203192 A EP 96203192A EP 0777151 B1 EP0777151 B1 EP 0777151B1
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EP
European Patent Office
Prior art keywords
group
ring
coupler
groups
bonded
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.)
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EP19960203192
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German (de)
English (en)
French (fr)
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EP0777151A3 (enrdf_load_stackoverflow
EP0777151A2 (en
Inventor
Barbara Boland Lussier
John Dicillo
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US08/680,191 external-priority patent/US5677114A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0777151A2 publication Critical patent/EP0777151A2/en
Publication of EP0777151A3 publication Critical patent/EP0777151A3/xx
Application granted granted Critical
Publication of EP0777151B1 publication Critical patent/EP0777151B1/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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds

Definitions

  • This invention relates to color photographic materials or elements comprising a yellow dye-forming coupler which forms a dye upon development which exhibits improved stability against dye fade upon exposure to light.
  • a typical photographic element contains multiple layers of light-sensitive photographic silver halide emulsions with one or more of these layers being spectrally sensitized to blue light, green light, and red light, respectively.
  • the blue, green, and red light sensitive layers will typically contain yellow, magenta or cyan dye forming couplers, respectively.
  • image dyes are formed by the coupling reaction of these couplers with the oxidized product of the color developing agent.
  • image couplers are selected to provide image dyes with good stability towards heat and light and which desirably have an absorption curve with a suitable peak absorption and low unwanted side absorptions in order to provide color photographic images with good color reproduction.
  • the present invention is concerned with improving the light stability of yellow image dyes. Couplers that form yellow dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Patent Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506, 3,447,928, 4,022,620, 4,443,536, and "Farbkuppler-eine LiteratureUbersicht,” published in Agfa Mitannonen, Band III, pp. 112-126 (1961). Other examples of yellow dye-forming couplers are detailed in Research Disclosure No. 365, Item 36544, September 1994, Section X-B(6). Such couplers are typically open chain ketomethylene compounds.
  • yellow image dyes to resist light fade is important to the longevity of color images, especially those which are destined to be subject to constant daylight exposure such as professional portraits and the like. Yellow images will fade and images formed with yellow dye as a component may change color if the rate of fade for the yellow dye is not sufficiently matched with the other dyes of the photographic element.
  • U.S. Patent No. 4,248,962 relates to a pyrazolotriazole magenta dye-forming coupler designed to release a photographically useful group upon coupling.
  • the patent proposes a timing group which will undergo an intramolecular nucleophilic displacement reaction to release a photographically useful group.
  • coupler 44 which contains a ballast having an acetate substituent on a phenoxy group connected through a linking group to a phenyl ring in the ballast.
  • Japanese published application 56-30126 discloses acylacetanilide yellow couplers containing a 2-chloro-5-carboxy anilino ring. There is no disclosure therein that couplers of this type can provide an improvement in dye light stability.
  • a problem to be solved is to provide a yellow image dye-forming coupler which forms a dye upon development which exhibits improved stability upon exposure to light.
  • the coupler is one for which the dye light stability may be further improved by the addition of a stabilizing addenda.
  • the invention provides a photographic element comprising a light sensitive silver halide emulsion layer having associated therewith an open chain ⁇ -carbonyl acetanilide yellow dye-forming coupler having the formula: wherein
  • Each R 2 is a substituent on the phenoxy ring "A", and there may be present up to four of these substituents.
  • This substituent may be broadly selected from those substituents which have a Hammett's sigma value of 0 or less. Hammett's sigma values are provided in C. Hansch and A. J. Leo, "Substituent Constants for Correlation Analysis in Chemistry and Biology", Wiley, New York, N.Y., 1979. Generally, values less than 0 indicate that a substituent has an electron donating effect relative to hydrogen. Thus, R 2 is electron donating. It is further provided that at least one R 2 group is located ortho to the acyloxy group containing R 1 . This group desirably contains branching.
  • R 2 is an alkyl, alkoxy or amino compound. Satisfactory compounds include thioalkyl, dialkylamino, and branched alkyl and alkoxy groups. Appropriate examples include t-butyl, t-pentyl, t-octyl, and isopropyl.
  • R 3 and R 4 substituents bonded to each of the n carbon atoms may be independently selected.
  • suitable R 3 and R 4 substituents may include alkyl, alkoxy (including polyalkoxy), aryl, aryloxy, heterocyclic, and amino groups. Alkyl or alkoxy groups of 1-18 carbon atoms and hydrogen are satisfactory substituents. If desired, R 3 or R 4 may form a ring with another R 3 or R 4 group.
  • R 5 is a substituent which may or may not be present as indicated by the subscript "p".
  • Each R 5 is a substituent which may be a halogen, an amino group, an alkyl group, or a group linked to the "B" ring by an provided that if L is other than wherein R is hydrogen or an alkyl group and R' is an alkylene group, then there is present at least one R 2 substituent on ring "A" ortho to the acyloxy group to which R1 is attached.
  • the photographic element of the invention forms a yellow image dye which exhibits an improved stability to light degradation.
  • R 1 is the substituent attached to the acyloxy group on the ring "A". It may be an alkyl, aryl, heterocyclic, or an amino group. Also, R 1 may form a ring bonded to another carbon atom which is a member of Ring "A". Desirably R 1 contains at least 4 carbon atom of oxygen or sulfur. Suitably, one or more of the R 5 substituents may occupy the 2-, 4-, or 6- position of the ring "B". Suitably, R 5 may be bonded to the ring "B” by an acyloxy, alkylthio, alkyl, amino, or oxy group.
  • Particularly suitable groups are alkylacyloxy, arylacyloxy, trifluoromethyl, alkylthio, alkoxy, aryloxy, alkyl, or amino groups.
  • the value of "p" may range from 0 to 3, suitably 1 to 3.
  • R 6 is an amino group, an alkyl group or an aryl group. More suitably, R 6 may be a secondary or tertiary alkyl group, a phenyl group, a phenyl amino group, or an alkyl amino group. Typically, the secondary alkyl group may be an isopropyl group, the tertiary alkyl group may be t-butyl, t-pentyl, t-octyl, or 1-methyl-1-cyclopropyl.
  • the phenyl group may be phenyl or phenyl substituted, for example, with alkoxy, alkyl or amido groups.
  • the amino may be a phenylamino or alkylamino group.
  • the group L is optionally present. As indicated by the value of q of up to three, there may be present as many as three L groups. Each of the L groups may be independently selected to provide a linkage between the ring "B" and the remainder of the coupler. In the broadest sense, L may be any divalent group linking the ballast directly or indirectly with a noncoupling position of the rest of the coupler. Each L may be represented, for example, by one of the groups: wherein R is hydrogen or an alkyl group and R' is an alkylene group. Specifically useful are: and
  • the group Z represents a heterocyclic group containing, a nitrogen atom in a five or six membered ring, wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring.
  • a heterocyclic group contain one or more nitrogen atoms in the ring and possibly an oxygen atom.
  • suitable groups are pyrazole, imidazole, hydantoin, urazole, and oxazole groups such as the following: wherein each R A , R B ,R C and R D is an independently selected group such as hydrogen, or an alkyl (e.g.
  • group Z may represent a heterocyclic group containing in a five or six membered ring one or two nitrogen atoms and possibly an oxygen atom, where the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring.
  • suitable groups are pyrazole, imidazole, hydantoin, succinimide, thiazole, thiazolidino, thiadiazole, saccharin, rhodanine, and oxazole groups such as the following: and wherein each R A , R B ,R C and R D is an independently selected group such as hydrogen, or an alkyl (e.g. methyl, ethyl ,propyl, phenylmethyl, sulfonamidoalkyl), aryl, or alkoxy (e.g. methoxy, ethoxy) group.
  • alkyl e.g. methyl, ethyl ,propyl, phenylmethyl, s
  • a benzotriazole group is useful as Z.
  • arylthio such as phenylthio groups and aryloxy such as phenoxy groups.
  • substituent groups which may be substituted on molecules herein include any groups, whether substituted or unsubstituted, which do not destroy properties necessary for photographic utility.
  • group When the term "group" is applied to the identification of a substituent containing a substitutable hydrogen, it is intended to encompass not only the substituent's unsubstituted form, but also its form further substituted with any group or groups as herein mentioned.
  • the group may be halogen or may be bonded to the remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous, or sulfur.
  • the substituent may be, for example, halogen, such as chlorine, bromine or fluorine; nitro; hydroxyl; cyano; carboxyl; or groups which may be further substituted, such as alkyl, including straight or branched chain alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl, 3-(2,4-di- t -pentylphenoxy) propyl, and tetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di- t -pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such as phenyl, 4- t -butylphenyl
  • substituents may themselves be further substituted one or more times with the described substituent groups.
  • the particular substituents used may be selected by those skilled in the art to attain the desired photographic properties for a specific application and can include, for example, hydrophobic groups, solubilizing groups, blocking groups, releasing or releasable groups, etc.
  • the above groups and substituents thereof may include those having up to 48 carbon atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but greater numbers are possible depending on the particular substituents selected.
  • the photographic element can be used in conjunction with an applied magnetic layer as described in Research Disclosure , November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND, and as described in Hatsumi Kyoukai Koukai Gihou No. 94-6023, published March 15, 1994, avaliable from the Japanese Patent Office, the contents of which are incorporated herein by reference.
  • inventive materials in a small format film, Research Disclosure , June 1994, Item 36230, provides suitable embodiments.
  • the silver halide emulsion containing elements employed in this invention can be either negative-working or positive-working as indicated by the type of processing instructions (i.e. color negative, reversal, or direct positive processing) provided with the element.
  • Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through V.
  • Various additives such as UV dyes, brighteners, antifoggants, stabilizers, light absorbing and scattering materials, and physical property modifying addenda such as hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections II and VI through VIII. Color materials are described in Sections X through XIII.
  • Scan facilitating is described in Section XIV.
  • Supports, exposure, development systems, and processing methods and agents are described in Sections XV to XX.
  • Desirable photographic elements and processing steps including other components suitable for use in photographic elements of the invention are also described in Research Disclosure , Item 37038, February 1995.
  • the processing step described above provides a negative image.
  • the described elements can be processed in the known Kodak C-41 color process as described in The British Journal of Photography Annual of 1988, pages 191-198. Where applicable, the element may be processed in accordance with color print processes such as the RA-4 process of Eastman Kodak Company as described in the British Journal of Photography Annual of 1988, Pp 198-199.
  • Such negative working emulsions are typically sold with instructions to process using a color negative method such as the mentioned C-41 or RA-4 process.
  • the color development step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and followed by uniformly fogging the element to render unexposed silver halide developable.
  • a non-chromogenic developing agent to develop exposed silver halide, but not form dye
  • uniformly fogging the element to render unexposed silver halide developable Such reversal emulsions are typically sold with instructions to process using a color reversal process such as E-6.
  • a direct positive emulsion can be employed to obtain a positive image.
  • Preferred color developing agents are p-phenylenediamines such as:
  • Development is usually followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver or silver halide, washing, and drying.
  • couplers of the invention are accomplished using conventional reactions.
  • the following is a typical method for preparing coupler Y-2 of the invention which may be employed in an analogous manner to prepare other couplers of the invention.
  • Methyl-4,4-dimethyl-3-oxovalerate (15.8 g, 0.1 mol) and 2-methoxy-5-nitroaniline (16.8 g, 0.01 mol) were taken up in toluene (150 mL) in a round bottomed flask fitted with a Dean-Stark trap. The mixture was heated to a vigorous reflux while the MeOH side-product was distilled off and removed. After 4 hours, the mixture was cooled and the toluene removed in vacuo. The residue was recrystallized from acetonitrile to yield 27 g of the desired condensation product.
  • Dispersions of the couplers were prepared in the following manner, exemplified with representative coupler Y2.
  • 1.55 g of the coupler, Y2, 0.72g of dibutyl phthalate, 0.6g of 2-(2-butoxyethoxy)ethyl acetate and 4.6g of ethylacetate were combined and warmed to 60°C to dissolve.
  • 21.2g of 11.55% gelatin, 2.44g of Alkanol XCTM (surfactant and trademark of E. I. Dupont Co., USA) and 9.62g of water were combined and warmed to 40°C. The two mixtures were combined and passed three times through a Gaulin colloid mill.
  • the photographic elements were prepared by coating the following layers in the order listed on a resin-coated paper support: 1st layer Gelatin 3.23 g/m 2 2nd layer Coupler dispersion 8.8 x 10 -4 mole coupling moieties/m 2 AgCl emulsion 0.28g Ag/m 2 and blue-sensitized 3rd layer Gelatin 1.4 g/m 2 Bis (vinylsulfonylmethyl)ether 0.14 g/m 2
  • the photographic elements were subjected to stepwise exposure to blue light and processed as follows at 35° C: Color Developer 45 seconds Bleach-Fix 45 seconds Wash (running water) 90 seconds
  • the developer and bleach-fix were of the following compositions: Developer Water 700 mL Triethanolamine 12.41 g Blankophor REU TM (Mobay Corp) 2.3 g Lithium polystyrene sulfonate (30%) 0.3 g N,N-diethylhydroxylamine (85%) 5.4 g Lithium sulfate 2.7 g N- ⁇ 2-[(4-amino-3-methylphenyl)ethylamino]-ethyl ⁇ -methanesulfonamide, sesquisulfate 5.0 g 1-hydroxyethyl-1,1-diphosphonic acid (60%) 0.81 g Potassium carbonate, anhydrous 21.16 g Potassium chloride 1.6 g Potassium bromide 7.0 g Water to make 1.0 L pH at 26.7°C adjusted to 10.2 Bleach-Fix Water 700 mL Solution of Ammonium thiosulfate(56.4% plus Ammonium sulfite (4%)
  • Yellow dyes were formed upon processing of the photographic elements.
  • the coatings were assessed sensitometrically for the following characteristics:
  • the comparative couplers were as follows:
  • Couplers C-1 and C-2 represent couplers actually in use in commercial photographic film. Couplers C-3 and C-4 are provides as additional comparisons.
  • the coating strips were exposed to a high intensity Xenon light source at a luminous flux level of 50 Klux with a WRATTEN 2C filter interposed between the light source and sample. After 2 weeks and 4 weeks, the strips were removed and the decrease in density from initial densities of 1.7, 1.0 and 0.5 were measured. The data is recorded in Table 2 as a measure of the per cent dye retained for each sample dye.
  • the couplers of the invention have superior light fastness as compared to couplers C-1 and C-2 typically used in the art and are advantageous over comparisons C-3 and C-4.
  • the amount of dye remaining after exposure averages 82.6% for the inventive couplers compared to an average of 43.5% for the comparative couplers. At 14 days the corresponding values are 93.8 and 73.0, respectively.
  • the inventive couplers are stable enough that they can be used without light stabilizing addenda when a neutral fade position with typical magenta and cyan dyes is desired.
  • Neutral fade could also be achieved even if extremely stable magenta and cyan dyes were utilized by incorporating light stabilizing addenda along with the yellow couplers of this invention in an analogous photographic format to that described above with the following weight ratios:
  • Yellow coupler coupler solvent such as dibutylphthalate : auxiliary solvent such as 2-(2-butoxyethoxy)ethylacetate : stabilizer addenda 54:15:18:13.
  • the stabilizer addenda typically used are those exemplified by compounds 1-3 but are not limited to these.
  • polymeric stabilizing addenda are also suitable.
  • the polymers can be homopolymers or copolymers which are miscible with the coupler and coupler solvent which are present, for example, as a latex or as an organic solution.
  • Table III describes 2-week and 4-week light fade data for dyes formed from representative couplers using compound 1 as stabilizing addenda. Coupler + Compound 1 Coupler Type Dye Retained from Initial Density 1.0 14 day 28 day Y-1 Inv 97% 90% Y-2 Inv 100% 93% Y-3 Inv 96% 86% Y-4 Inv 93% 84% Y-5 Inv 93% 90% Y-6 Inv 95% 85% C-1 Comp 88% 69% C-3 Comp 91% 71%
  • the couplers of this invention yield dyes which show highly superior resistance to light fade when coated with stabilizing addenda.
  • Coupler Y-2 was coated in a format similar to that described above with the weight ratio of coupler : dibutylphthalate : stabilizing addenda of 3:2:1.
  • Emulsion addenda ADD-1 was present in the emulsion in the amount of 0.88 mg/ft 2 .
  • Table IV thus show that coupler Y-2 is still quite stable even without stabilizing addenda and can be made even more stable in the presence of stabilizing addenda.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19960203192 1995-11-30 1996-11-15 Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process Expired - Lifetime EP0777151B1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US680191 1984-12-10
US56551795A 1995-11-30 1995-11-30
US565517 1995-11-30
US68074396A 1996-07-15 1996-07-15
US680743 1996-07-15
US08/680,191 US5677114A (en) 1995-11-30 1996-07-15 Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process

Publications (3)

Publication Number Publication Date
EP0777151A2 EP0777151A2 (en) 1997-06-04
EP0777151A3 EP0777151A3 (enrdf_load_stackoverflow) 1997-07-02
EP0777151B1 true EP0777151B1 (en) 2000-05-31

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EP19960203192 Expired - Lifetime EP0777151B1 (en) 1995-11-30 1996-11-15 Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process

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EP (1) EP0777151B1 (enrdf_load_stackoverflow)
JP (1) JPH09179259A (enrdf_load_stackoverflow)
DE (1) DE69608648T2 (enrdf_load_stackoverflow)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9717166D0 (en) * 1997-08-14 1997-10-22 Eastman Kodak Co Image dye-forming couplers and photographic elements containing them

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB536939A (en) 1939-08-24 1941-06-03 Eastman Kodak Co Improvements in and relating to photographic colour development
US2407210A (en) 1944-04-14 1946-09-03 Eastman Kodak Co Color couplers
BE543742A (enrdf_load_stackoverflow) 1954-12-20
US3048194A (en) 1958-11-26 1962-08-07 Gen Fire Extinguisher Corp Fire extinguisher head assembly
US3265506A (en) 1964-05-04 1966-08-09 Eastman Kodak Co Yellow forming couplers
US3447928A (en) 1965-07-26 1969-06-03 Eastman Kodak Co Silver halide emulsion containing twoequivalent yellow dye-forming coupler
JPS51102636A (en) 1974-04-03 1976-09-10 Fuji Photo Film Co Ltd Karaashashingazo no keiseihoho
US4248962A (en) 1977-12-23 1981-02-03 Eastman Kodak Company Photographic emulsions, elements and processes utilizing release compounds
JPS5630126A (en) * 1979-08-20 1981-03-26 Konishiroku Photo Ind Co Ltd Silver halide photographic material
US4443536A (en) 1981-08-25 1984-04-17 Eastman Kodak Company Nondiffusible photographic couplers and photographic elements and processes employing same

Also Published As

Publication number Publication date
DE69608648D1 (de) 2000-07-06
DE69608648T2 (de) 2001-02-08
JPH09179259A (ja) 1997-07-11
EP0777151A3 (enrdf_load_stackoverflow) 1997-07-02
EP0777151A2 (en) 1997-06-04

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