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
  • G03C7/327—Macromolecular coupling substances
  • G03C7/3275—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• This invention relates to silver halide color photographic materials containing polymeric dye-forming couplers.
• the coupler has been formed by emulsion polymerization of ethylenically unsaturated monomers in the presence of a high-boiling organic coupler solvent.
• color photographic images can be formed by reaction between oxidized silver halide developing agent and a dye forming coupler.
• a coupler of the acylacetanilide or benzoylacetanilide type generally is used for forming a yellow dye image
• a coupler of the pyrazolone, pyrazoloazole, pyrazolobenzimidazole, cyanoacetophenone or indazolone type is generally used for forming a magenta dye image
• a phenolic or naphtholic coupler is generally used for forming a cyan dye image.
• polymeric couplers can be enhanced if they are prepared by an emulsion polymerization process in the presence of a high-boiling organic solvent, commonly known as a coupler solvent.
• this invention relates to a photographic element comprising a support, a silver halide emulsion layer, and a polymeric coupler wherein the polymeric coupler is an addition polymer of an ethylenically unsaturated monomer containing a dye-forming coupler moiety prepared by emulsion polymerization in the presence of a high-boiling organic coupler solvent.
• the present invention relates to a process for the preparation of polymeric couplers which comprises emulsion polymerization of ethylenically unsaturated monomers containing a dye-forming coupler moiety, the polymerization being carried out in the presence of a high-boiling organic coupler solvent.
• the coupler solvents useful in the emulsion polymerization process according to this invention are known water-immiscible organic solvents having a boiling point above about 200°C.
• Useful high-boiling organic solvents include phthalic acid alkyl esters such as dibutyl phthalate and dioctyl phthalate; phosphoric acid esters such as tricresyl phosphate, diphenyl phosphate, triphenyl phosphate, tris-2-ethylhexyl phosphate, tris-3,5,5-trimethylhexyl phosphate, and dioctyl butyl phosphate; citric acid esters such as tributyl acetylcitrate; benzoic acid esters such as octyl benzoate; dibasic aliphatic esters such as dibutoxyethyl succinate and dioctyl azelate; trimesic acid esters such as tributyl trimesate; aliphatic amides such as N,N-diethyl lauramide and 1,4-cyclohexanedimethylene-bis-(2-ethyl
• Preferred solvents include di-n-butyl phthalate, tricresyl phosphate, tris-2-ethylhexyl phosphate, tris-3,5,5-trimethylhexyl phosphate, 2,4-di-tert-pentyl-phenol, and N,N-diethyl lauramide.
• Any emulsion polymerized polymeric couplers derived from an ethylenically unsaturated dye-forming coupler moiety known in the art can be prepared in accordance with this invention.
• Preferred ethylenically unsaturated coupler moieties which can be copolymerized with other suitable non-dye-forming monomers are illustrated by the following structures:
• the polymeric couplers of this invention can be homopolymers derived from coupler containing monomers, or they can be copolymerized with one or more other suitable ethylenically unsaturated monomers including, for example, acrylic acid, methacrylic acid, acrylic acid esters, acrylic acid amides, vinyl esters, acrylonitrile, methacrylonitrile, aromatic vinyl compounds, vinylene chloride, itaconic acid and itaconic acid monoesters, citraconic acid, crotonic acid, maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine, vinyl alkyl esters such as methyl, ethyl, butyl and aryl esters such as phenyl esters.
• suitable ethylenically unsaturated monomers including, for example, acrylic acid, methacrylic acid, acrylic acid esters, acrylic acid amides, vinyl esters, acrylonitrile, methacrylonitrile, aromatic vinyl compounds,
• the polymeric coupler contains an acrylate, methacrylate, acrylamide or methacrylamide polymer backbone and further comprises repeating units derived from non-coupler containing comonomers selected to provide useful physical and chemical properties for the polymeric coupler, such as useful solubility, compatibility with other components of the photographic material, stability and flexibility.
• the polymeric backbone of the polymeric couplers of the invention includes the alkoxyacrylate comonomers disclosed in Lau et al. U.S. Patent No. 4,612,278 issued September 16, 1986.
• polymeric couplers of this invention can be used in the ways and for the purposes that polymeric couplers are used in the photographic art. They may be used in any concentration which is effective for the intended purpose. Generally, good results are obtained using concentrations ranging from 10 ⁇ 4 to 0.5 mole of polymeric coupler per mole of silver in the photographic element.
• Photographic elements in which the polymeric couplers of this invention are incorporated can be a simple element comprising a support and a single silver halide emulsion layer or they can be multilayer, multicolor elements.
• the polymeric couplers of this invention can be incorporated in the silver halide emulsion layer or in another layer, such as an adjacent layer, where they will come into reactive association with oxidized color developing agent which has been formed by the development of silver halide in the emulsion layer.
• the silver halide emulsion layer can contain, or have associated with it, other photographic coupler compounds, such as color forming couplers, colored masking couplers, competing couplers, DIR-couplers, DIAR-couplers, and the like. These other photographic coupler compounds can form dyes of the same or different color and hue as the polymeric coupler compounds of this invention.
• the silver halide emulsion layer can contain addenda conventionally contained in such layers.
• a typical photographic element of the invention comprises a support having thereon a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, 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 that least one yellow dye-forming coupler, at least one of the couplers in the element being a polymeric coupler as defined herein.
• the element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like.
• the photographic elements of this invention or individual layers thereof can be chemically sensitized, as described in Section III; contain brighteners, as described in Section V; antifoggants and stabilizers, as described in section VI; antistain agents and image dye stabilizers, as disclosed in Section VII, Paragraphs I and J; light absorbing and scattering materials, as described in Section VIII; hardeners, as described in Section XI; plasticizers and lubricants, as described in Section XII; antistain agents, as described in Section XIII; matting agents, as described in Section XVI; and development modifiers, as described in Section XXI of the Research Disclosure.
• the photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described herein.
• the elements can contain a high-boiling organic solvent added after completion of the coupler polymerization reaction to modify the physical properties of the elements' layers, as is disclosed in, e.g., U.S. Patent No. 4,511,647 issued April 16, 1985. Any such optionally added high-boiling organic solvents may be the same as or different from one that is present during the coupler polymerization reaction in accordance with this invention.
• 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 oxidize the color developing agent. Oxidixed color developing agent in turn reacts with the coupler to yield a dye.
• the polymeric couplers prepared by the method according to this invention are useful in combination with other couplers, such as monomeric and/or polymeric couplers known in the photographic art, such as those 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 polymeric couplers of this invention can be made by following procedures generally known in the organic compound synthesis art.
• the polymeric couplers are prepared by emulsion polymerization of suitable ethylenically unsaturated monomers in the presence of a high boiling solvent as described herein, and then dispersed in an aqueous gelatin solution.
• Suitable emulsion polymerization methods are disclosed in, for example, U.S. Patent. Nos. 3,370,952; 4,080,211; and 4,612,278 .
• the procedures described in these patents are modified at least to the extent that a high-boiling coupler organic solvent is incorporated in the reaction mixture prior to or during polymerization.
• the polymerizable monomers and the coupler solvent are combined with water and an emulsifier, such as a surfactant, and then polymerized at elevated temperature by the addition of a catalyst, such as ammonium persulfate/sodium bisulfate; dimethyl 2,2′-azobisisobutyrate; 2,2′-azobisisobutyronitrile; 2,2′-azobis(amidino propane) dihydrochloride.
• a catalyst such as ammonium persulfate/sodium bisulfate; dimethyl 2,2′-azobisisobutyrate; 2,2′-azobisisobutyronitrile; 2,2′-azobis(amidino propane) dihydrochloride.
• the equivalent weight and the ratio of coupler monomer (a) to acrylate monomer (b) were obtained from chlorine analysis; the amount of di-n-butylphthalate incorporated into the latex particles was determined by high pressure liquid chromatographic (HPLC) analysis.
• HPLC high pressure liquid chromatographic
• the mixture was thouroughly mixed and then treated in a Waring blender for 30 seconds.
• the emulsified mixture was then transferred to a 1-liter, 3-necked flask set in a 90 ° C. constant temperature water bath.
• To this mixture were added 12 ml (0.0012 mole) of an aqueous solution (0.1 mole/liter) of sodium bisulfite, followed by the dropwise addition of 12 ml (0.0012) of an aqueous solution (0.1 mole/­liter) of ammonium persulfate. Stirring was continued for two hours, after which all of the starting coupler monomer (a) was shown by TLC to have been consumed.
• the pH of the latex was adjusted from 3.5 to 6.0 with sodium hydroxide.
• the latex was filtered and dialized for two days. A sample was freeze-dried for analysis.
• the equivalent weight and the ratio of coupler monomer (d) to acrylate monomer (b) were obtained from chlorine analysis; the amount of N,N-diethyllauramide incorporated into the latex particles was determined by HPLC analysis.
• the polymeric coupler prepared in the presence of a high-boiling coupler solvent provided a higher maximum dye density than the comparison polymeric coupler prepared in the absence of such solvent.
• Element 5 contained the comparison coupler of Example 1 which had been combined with 50% by weight of the coupler solvent di-n-butyl phthalate after completion of the polymerization reaction and prior to the coupler's incorporation in the coating composition.
• Element 6 contained Coupler C of the invention as identified in Example 1. The results are shown in Table 2. TABLE 2 Element No. D max 5 Comparison 2.09 6 Coupler C 2.29
• Table 3b show the effectiveness of a variety of different high-boiling coupler. solvents in producing images having improved maximum densities, even where the proportion of incorporated solvent is low.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (5)

Citations (2)

• 1989
  • 1989-04-27 JP JP10609489A patent/JPH0213943A/ja active Pending
  • 1989-05-08 EP EP19890304602 patent/EP0341088B1/fr not_active Expired - Lifetime

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