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
  • G03C7/30523—Phenols or naphtols couplers

Definitions

• the present invention relates to a novel phenolic cyan dye-forming coupler and to a photographic element containing such coupler.
• Couplers which are used to obtain cyan dyes for color photography are typically phenols and naphthols. These couplers yield azomethine dyes upon coupling with oxidized aromatic primary amino color developing agents.
• U. S. Patent 4,333,999 describes cyan phenolic couplers which comprise a p-cyanophenyl­ureido group in the 2-position of the phenolic ring.
• This class of couplers has found wide commercial acceptance in photographic applications. Included among the important advantages of these couplers is their ability to provide dyes of excellent purity and hues which are shifted bathochromically to the long wavelength red absorption region.
• Couplers which have found extensive utility, further improvements in coupler reactivity and enhanced dye absorption continue to be sought. For example, it has been difficult to obtain, with the same coupler, both high coupling effectiveness and a dye of the desired hue purity with long wavelength red absorption. Coupling effectiveness is measured for each coupler of this invention by comparing the gamma or contrast of its dye image sensitometric test curve with that of a control coupler under identical conditions.
• the present invention seeks to meet these objectives by providing a cyan phenolic coupler compound, and a photographic element containing such compound, wherein the 5-position acylamino ballast moiety of the compound includes the use of substituent groups defined as R1, R2 and X, in the Formula described below to provide steric bulk in the ballast portion of the coupler compound as well as in the resulting dye molecule.
• the invention provides a coupler compound, and a photographic element comprising such compound, characterized in that the compound has the following structural formula: wherein R1 is an unsubstituted or substituted alkyl group having from 1 to about 24 carbon atoms, an unsubstituted or substituted aralkyl group having from 7 to about 24 carbon atoms or an unsubstituted or substituted cycloalkyl group having from 3 to about 8 carbon atoms in the ring; R2 is hydrogen or a straight or branched chain, unsubstituted or substituted alkyl group having from 1 to about 16 carbon atoms; L is oxygen or sulfur; X is hydrogen, an unsubstituted or substituted primary, secondary or tertiary alkyl group having from 1 to about 24 carbon atoms, an unsubstituted or substituted aryl group having from 6 to about 24 carbon atoms, an unsubstituted or substituted cycloalkyl group having from 3 to about 8 carbon
• R1 is an aralkyl group
• the alkylene portion thereof preferably comprises 1 or 2 carbon atoms.
• Preferred R1 groups are unsubstituted or substituted alkyl groups of 1 to about 10 carbon atoms or cycloalkyl of 4 to about 7 carbon atoms Cycloalkyl or branched chain alkyl groups are preferred over straight chain alkyl, since they provide greater steric interaction with adjacent groups thus enhancing the desired properties of the described coupler compounds.
• Experimental data has shown that when both R1 and R2 are hydrogen the desired improvement in photographic properties is not realized.
• Substituents which may be present on the R1 and R2 groups include hydroxy, halogen, CF3, CN, NO2 and amino, including subsituted amino, of the formula NR a R b , where R a and R b , which may be the same or different, are hydrogen, alkyl of 1 to about 6 carbon atoms or phenyl, which may be substituted, or R a and R b may be combined with the nitrogen atom to which they are attached to form a heterocyclic ring of 5 to 6 atoms.
• the X group when alkyl, cycloalkyl, aryl or a heterocyclic ring, and the Y group may also be substituted.
• substituents may be alkyl or alkoxy groups having from 1 to about 6 carbon atoms, or hydroxy, halogen, CF3, CN, NO2 or amino, including substituted amino as defined above in the R1 and R2 substituent definitions.
• Preferred X groups are secondary alkyl moieties containing 3 or 4 carbon atoms, chloro, cyano and nitro.
• Coupling off groups defined by Z are well known to those skilled in the art. Such groups can determine the equivalency of the coupler i.e., whether it is a two-equivalent coupler or a four-equivalent coupler. Such groups can also modify the reactivity of the coupler or can advantageously affect the layer in which the coupler is coated, or other layers in the element by performing, after release from the coupler, such functions as development inhibition, bleach inhibition, bleach acceleration, color correction and the like.
• Typical coupling-off groups are -OR3, -NHSO2R3, -OP(OR3)2 and -O-Q-R3 wherein Q is -CO-, -COO-, -SO2- or -CONR4.
• Preferred coupling-off groups include those having the formula: -OR5, -OCOR5, -OCO2R5, -NHSO2R5, -OP(OR5)3, -OCON(R5)2, -OSO2R5, -OCH2CONHAlkB or -OAlkNHSO2R5 where R5 is alkyl having from 1 to about 16 carbon atoms or aryl having from 6 to about 18 carbon atoms; Alk is alkylene having from 1 to about 3 carbon atoms and B is -OH, -OR5 or -OCOR5.
• the ballast portion of the above-described coupler structure which is defined by the moiety: is of such size and configuration as to confer on the coupler molecule sufficient bulk to render the coupler substantially non-diffusible from the layer in which it is coated in a photographic element.
• Such ballasting is achieved when one or more of the R1, R2, X or Y groups, as defined above, includes substituted or unsubstituted alkyl or aralkyl groups containing at least 7 and up to about 24 carbon atoms. Representative substituents can be as described above for the R1, R2, X and Y groups.
• the desirable objectives of this invention are attained by particular combinations of substituent groups on the ballast moiety of the coupler compounds of this invention.
• bulky substituent groups are present in at least two of the positions represented by R1, R2 and X, which substituents are spatially arranged so that steric interaction between them, or with adjacent portions of the coupler or the dye molecule formed therefrom, result in cyan dyes having desirably narrow bandwidths while absorbing red light at relatively longer wavelengths.
• Preferred coupler compounds of this invention include those presented by the structural formula: wherein: Z is hydrogen or L is oxygen or sulfur; R6 is an alkyl or alkoxy group having from 1 to about 10 carbon atoms; R1 is an unsubstituted or a substituted alkyl group having from 1 to about 10 carbon atoms; R2 is hydrogen or an alkyl group having from 1 to about 10 carbon atoms; X is a secondary alkyl group having from 3 to about 18 carbon atoms, alkylcarbonyl, alkoxycarbonyl, alkanesulfonyl or alkanesulfonamido where the alkyl, alkane or alkoxy moieties have from 3 to about 18 carbon atoms, or X is chloro, cyano or nitro, or X is hydrogen when i) R1 is aralkyl having from 7 to about 10 carbon atoms or branched chain alkyl having from 3 to about 8 carbon atoms and ii) R2 is alky
• Especially preferred coupler compounds are those where Y is substituted in the 5-position of the phenyl ring.
• Couplers of this invention can be prepared by reacting p-cyanophenylisocyanate with an appropriate aminophenol, such as 2-amino-5-nitro­phenol or 2-amino-4-chloro-5-nitrophenol to form the 2-(p-cyanophenyl)ureido compound.
• the nitro group can then be reduced to an amine and the ballast group attached thereto by conventional procedures.
• Two equivalent couplers can be prepared by known techniques, for example, by substitution of the 4-chloro group on the starting phenol.
• Coupler Compound No. 1 Preparation of Coupler Compound No. 1 was carried out according to the following scheme:
• Coupler S-18 was dissolved in 800 ml tetrahydrofuran and shaken 7 hours with 6 g 10% palladium on carbon catalyst under 40 lb hydrogen pressure. Removal of catalyst, followed by concentration and crystallization from acetonitrile yielded 50 g of colorless Coupler No. 1, m.p. 175-177°.
• Coupler No. 2 (183-185°), Coupler No. 3 (105-107°), Coupler No. 5 (191-192°), and Coupler No. 6 (138-140°).
• cyan dye-forming couplers of this invention can be used in the ways and for the purposes that cyan dye-forming couplers are used in the photographic art.
• the couplers are incorporated in silver halide emulsions and the emulsions coated on a support to form a photographic element.
• the couplers can be incorporated in photographic elements adjacent the silver halide emulsion layer where, during development, the coupler will be in reactive association with development products such as oxidized color developing agent.
• the term "in reactive association” signifies that the coupler is in a silver halide emulsion layer or in an adjacent layer where, during processing, it is capable of reacting with silver halide development products.
• the photographic elements can be single color elements or multicolor elements.
• the cyan dye-forming coupler is ususally associated with a red-sensitive emulsion, although it could be associated with an unsensitized emulsion or an emulsion sensitized to a different region of the spectrum.
• Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
• the layers of the element, including the layers of the image-forming units, can be arranged in various order as known in the art.
• a typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, at least one of the cyan dye-forming couplers being a coupler of this invention, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.
• the element can contain additional layers, such as filter layer, interlayers, overcoat layers, subbing layers, and the like.
• the silver halide emulsions employed in the elements of this invention can be either negative-working or positive-working. Suitable emulsions and their preparation are described in Research Disclosure Sections I and II and the publications cited herein. Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure Section IX and the publications cited herein.
• the elements of the invention can include additional couplers as described in Research Disclosure Section VII, paragraphs D, E, F and G and the publications cited therein. These couplers can be incorporated in the elements and emulsions as described in Research Disclosure Section VII, paragraph C and the publications cited therein.
• the photographic elements of this invention can contain brighteners (Research Disclosure Section V), antifoggants and stabilizers (Research Disclosure Section VI), antistain agents and image dye stabilizers (Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (Research Disclosure Section VIII), hardeners (Research Disclosure Section XI), plasticizers and lubricants (Research Disclosure Section XII), antistatic agents (Research Disclosure Section XIII), matting agents (Research Disclosure Section XVI) and development modifiers (Research Disclosure Section XXI).
• the photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.
• Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX.
• Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and to oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
• Preferred color developing agents are p-phenylene diamines.
• 4-amino-3-methyl-N,N-diethylaniline hydrochloride 4-amino-3-methyl-N-ethyl-N- ⁇ -(methanesulfonoamido)-­ethylaniline sulfate hydrate, 4-amino-3-methyl-N-­ethyl-N- ⁇ -hydroxyethylaniline sulfate, 4-amino-­3- ⁇ -(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxy-­ethyl)-m-toluidine di-p-toluene sulfonic acid.
• this processing step leads to a negative image.
• this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniform fogging of the element to render unexposed silver halide developable.
• a direct positive emulsion can be employed to obtain a positive image.
• Coupler A is identical to coupler number 7, in Table I, of U.S. Patent 4,333,999, the structural formula for which is noted below.
• Hue measurements on a normalized spectral absorption curve included ⁇ max (the peak absorption wavelength) and HBW (the half-bandwidth).
• the HBW value serves to indicate the degree of unwanted absorption tailing into the green region.
• Particularly useful couplers provided dye images with G > 1.00, ⁇ max > 680 nm and HBW ⁇ 145 nm.
• Photographic elements were prepared by coating a cellulose acetate-butyrate film support with a photosensitive layer containing a silver bromoiodide emulsion at 0.91 g Ag/m2, gelatin at 3.78 g/m2, and a cyan phenolic coupler, as identified below, dispersed in one-half its weight of di-n-butyl phthalate and coated at 1.62 x 10 ⁇ 3 moles/m2.
• the photosensitive layer was overcoated with a layer containing gelatin at 1.08 g/m2 and the hardener compound bis-vinylsulfonylmethyl ether at 1.75 weight percent based on total gelatin.
• Comparison Couplers A and B of Table II represent structures in which the Y values do not conform to the requirements of the present invention. As shown in Table II, couplers of this invention provide improved coupler effectiveness (G) with improved hue purity (HBW) while preserving the desirably high ⁇ max absorption values.

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• 1987
  • 1987-12-09 EP EP87310810A patent/EP0271323A3/en not_active Withdrawn
  • 1987-12-12 JP JP62313175A patent/JPH0682200B2/ja not_active Expired - Lifetime

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