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
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
  • G03C7/3005—Combinations of couplers and photographic additives
  • G03C7/3008—Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
• • 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
• • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39212—Carbocyclic
  • G03C7/39216—Carbocyclic with OH groups

Definitions

• the present invention relates to photographic coupler compositions which comprise a magenta dye-forming coupler and a hydroxy benzoate compound which increases the activity of the dye-forming coupler.
• the invention also relates to silver halide color photographic materials including such coupler compositions.
• 61-075349 discloses photographic silver halide emulsion layers containing a coupler dissolved in a phenolic organic solvent having a high boiling point.
• the Aoki et al U. S. Patent No. 4,686,177 discloses silver halide color photographic materials containing a cyan coupler which may be dissolved in an organic solvent. The resulting solution is finely dispersed in water or an aqueous binder for incorporation in the photographic material.
• Aoki et al broadly disclose numerous organic solvents which may be employed including, among others, alcohols and phenols.
• 137,722, 143,570 and 145,342 similarly disclose silver halide color photographic materials which include at least one magenta coupler and a non-color forming phenolic compound such as a phenolic high-boiling organic solvent.
• Japanese Published Patent Application No. 81-041098 discloses silver halide color photographic light sensitive materials prepared using cyan coupler compounds dispersed and emulsified in solvents having a boiling point greater than 200°C and saturated alcohols of the formula ROH wherein R is a 9 to 18 carbon containing saturated unbranched aliphatic group.
• the term improved coupler activity relates to the improved colorability of a coupler as indicated, for example, by the acceleration of the reaction of the coupler with the oxidized developer in forming the colored dye and/or by an increase in the color density of the resulting colored dye.
• the Sasaki et al U. S. Patent No. 4,774,166 broadly discloses numerous compounds for use as coloration accelerators for couplers which result in a reduction in the photographic processing time.
• preferred coloration accelerators comprise phenolic compounds, oxyalkylene compounds and hydroxy substituted, 5- to 7- membered heterocyclic ring compounds.
• Sasaki et al also broadly disclose the use of various high boiling point organic solvents in combination with the couplers, which solvents include, among others, phthalates, phosphates and benzoates.
• the Kimura et al U. S. Patent No. 4,551,442 also discloses silver halide photographic materials containing at least one cyan coupler and a phenolic compound which improves color image.
• the Snyder U. S. Patent No. 4,207,393 discloses compositions containing a coupler compound and a phenolic compound which acts as a contrast enhancer.
• coupler compositions are disadvantageous in that relatively large amounts of a coupler are required to provide satisfactory color density, the reaction rate of the coupler with the oxidized developer is unacceptably low, the coupler exhibits unacceptably high sensitivity to the pH of the developer solution and/or the like.
• the problem to be solved by this invention is to provide coupler compositions of improved activity for use in color photographic materials and methods.
• a more specific problem to be solved is to provide coupler compositions which exhibit improved coupler activity wherein improved coupler activity is indicated by an increased color density in a colored dye formed from the coupler composition.
• a further problem to be solved of the present invention to provide coupler compositions which exhibit improved coupler activity as indicated by an increase in the color density of the dye resulting from reaction of the coupler composition, without causing significant bathochromic hue shifts in the colored dye.
• the present invention provides photographic coupler compositions which comprise a magenta dye-forming coupler and a hydroxy benzoate compound in an amount sufficient to increase the activity of the dye-forming coupler.
• a photographic coupler composition comprising a magenta dye-forming coupler, and a hydroxy benzoate compound in an amount sufficient to increase the activity of the dye-forming coupler, the hydroxy benzoate compound being of the formula wherein the COOR1 substituent is located in the meta or para position with respect to the hydroxy group, R1 is selected from the group consisting of straight chain and branched chain alkyl groups, straight chain and branched chain alkenyl groups and straight chain and branched chain alkylene groups, and halogen-substituted derivatives of said alkyl, alkenyl and alkylene groups, R2 is selected from the group consisting of straight chain and branched chain alkyl groups, straight chain and branched chain alkoxy groups and a chlorine atom, and n is 0 or 1,
• a color photographic element comprising a silver halide emulsion and a coupler composition comprising a magenta dye-forming coupler and a hydroxy benzoate compound in an amount sufficient to increase the activity of the dye-forming coupler, the hydroxy benzoate compound being of the formula wherein the COOR1 substituent is located in the meta or para position with respect to the hydroxy group, R1 is selected from the group consisting of straight chain and branched chain alkyl groups, straight chain and branched chain alkenyl groups and straight chain and branched chain alkylene groups, and halogen-substituted derivatives of said alkyl, alkenyl and alkylene groups, R2 is selected from the group consisting of straight chain and branched chain alkyl groups, straight chain and branched chain alkoxy groups and a chlorine atom, and n is 0 or 1, provided that the total number of carbon atoms in R1 and R2 is from about 7 to about 24, and the magenta dye-
• the hydroxy benzoate compound employed in the coupler compositions of the present invention provides the magenta dye-forming coupler with increased activity as indicated by an increase in the color density of the colored dye formed therefrom, particularly without causing significant bathochromic hue shifts in the colored dye.
• the hydroxy benzoate compound is employed in combination with the magenta dye-forming coupler in order to increase the dye-forming coupler's activity.
• the coupler compositions of the present invention are therefore suitable for use in improved silver halide color photographic materials and in improved methods for the formation of color images.
• the hydroxy benzoate compounds which are employed in the coupler compositions of the present invention may serve as solvents for the coupler compounds and/or may be used as non-solvent additives. It is important that the hydroxy benzoate compounds employed in the present invention contain sufficient ballast to minimize their water solubility, volatility and diffusivity.
• Hydroxy benzoate compounds suitable for use in the coupler compositions of the present invention are of the formula wherein the COOR1 substituent is located in the meta or para position with respect to the hydroxy group, R1 is selected from the group consisting of straight chain and branched chain alkyl groups, alkenyl groups and alkylene groups, and halogen-substituted straight chain and branched chain alkyl, alkenyl and alkylene groups, each R2 is a straight or branched chain alkyl or alkoxy group or chlorine atom, and n is from 0 to 4, provided that the total number of carbon atoms in R1 and all R2's is from about 7 to about 24.
• the COOR1 substituent may be located in the meta or para position with respect to the hydroxy group. In a preferred embodiment, the COOR1 substituent is located in the para position with respect to the hydroxy group.
• R1 comprises a straight or branched chain alkyl group and contains at least 8 carbon atoms.
• the hydroxy benzoate compounds may contain from 0 to 4 of the R2 substituents. In preferred embodiments, the compounds contain no R2 substituents (n is zero) or a single R2 substituent (n is 1). In a further preferred embodiment, the total number of carbon atoms in R1 and all of the R2 substituents is from about 8 to about 18.
• hydroxy benzoate compounds particularly suitable for use in the compositions and methods of the present invention include, but are not limited to, 2-ethylhexyl-p-hydroxybenzoate, nonyl-p-hydroxybenzoate and dodecyl-p-hydroxybenzoate. Additional useful hydroxy benzoates include, but are not limited to, the following:
• the hydroxy benzoate compound employed in the coupler compositions of the present invention may act as a solvent for the dye-forming coupler.
• One or more additional organic solvents for the coupler compound may also be employed in the compositions of the present invention.
• conventional organic coupler solvents are known in the art and may be employed when the hydroxy benzoate compound of the present invention is used in an additive amount which is not sufficient to result in a solution of the coupler compound. Examples of conventional organic solvents which may be used in the present compositions are described in the Examples set forth below.
• the hydroxy benzoate compound is employed in the coupler compositions of the present invention in an amount sufficient to increase the activity of the dye-forming coupler. In most applications, it is preferred that the dye-forming coupler and the hydroxy benzoate compound are employed in a weight ratio of from about 1:0.1 to about 1:10 in order to effect an increase in the activity of the dye-forming coupler.
• the dye-forming coupler included in the present coupler compositions comprises a magenta dye-forming coupler.
• Couplers which form magenta dyes upon reaction with oxidized color developing agents are well known in the art and are described in such representative patents and publications as: U. S. Patents Nos.
• Preferred magenta dye-forming couplers comprise pyrazolone compounds of the general formulae: pyrazolotriazole compounds of the general formulae: and pyrazolobenzimidazoles of the formula: wherein Ar is an unsubstituted aryl group or an aryl group (including pyridyl) substituted with one or more substituents selected from halogen atoms and cyano, alkylsulfonyl, arylsulfonyl, sulfamoyl, sulfonamido, carbamoyl, carbonamido, alkoxy, acyloxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, ureido, nitro, alkyl, and trifluoromethyl, or Ar is an aryl group substituted with a group which forms a link to a polymeric chain; R1 is a substituted or unsubstituted phenyl group and R2 is a
• Coupling-off groups are well known to those skilled in the photographic art. Generally, such groups determine the equivalency of the coupler and modify the reactivity of the coupler. Coupling-off groups can also advantageously effect the layer in which the coupler is coated or other layers in the photographic material by performing, after release from the coupler, such functions as development inhibition, bleach acceleration, color correction, development acceleration and the like.
• Representative coupling-off groups include, as noted above, halogens (for example, chloro), alkoxy, aryloxy, alkyl thio, aryl thio, acyloxy, sulfonamido, carbonamido, arylazo, nitrogen-containing heterocyclic groups such as pyrazolyl and imidazolyl, and imido groups such as succinimido and hydantoinyl groups. Except for the halogens, these groups may be substituted if desired. Coupling-off groups are described in further detail in: U. S. Patents Nos.
• a coupler compound should be nondiffusible when incorporated in a photographic element. That is, the coupler compound should be of such a molecular size and configuration that it will exhibit substantially no diffusion from the layer in which it is coated.
• the total number of carbon atoms contained in R1, or R2, or R3 and R4 combined should be at least 6.
• R1, or R2, or R3 and R4 combined contain from 6 to about 30 carbon atoms.
• R1, or R2, or R3 or R4 may serve as a link to or form part of a polymeric chain.
• the magenta dye-forming coupler is of the formula M-1 and Ar is of the formula wherein R5 is selected from the group consisting of halogen atoms and cyano, alkylsulfonyl, arylsulfonyl, sulfamoyl, sulfonamido, carbamoyl, carbonamido, ureido, alkoxycarbonyl, aryloxycarbonyl, acyloxy, alkoxy, aryloxy, nitro and trifluoromethyl groups.
• R5 is selected from the group consisting of halogen atoms and cyano, alkylsulfonyl, arylsulfonyl, sulfamoyl, sulfonamido, carbamoyl, carbonamido, ureido, alkoxycarbonyl, aryloxycarbonyl, acyloxy, alkoxy, aryloxy, nitro and trifluoromethyl groups
• R1 is of the formula wherein p is from zero to 2 and each R6 is in a meta or para position with respect to R7; each R6 is individually selected from the group consisting of halogen atoms and alkyl, alkoxy, aryloxy, carbonamido, carbamoyl, sulfonamido, sulfamoyl, alkylsulfoxyl, arylsulfoxyl, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, ureido, imido, carbamate, heterocyclic, cyano, nitro, acyl, trifluoromethyl, alkylthio and carboxyl groups; and R7 is selected from the group consisting of hydrogen, halogen atoms and alkyl, alkoxy, aryloxy alkyl
• R7 is a chlorine atom or an alkoxy group.
• advantageous speed/fog positions can be achieved by using the above described hydroxy benzoate compounds with a coupler according to formula M-3 that is linked to a polymeric chain.
• Suitable magenta dye-forming couplers for use in the compositions and methods of the present invention include, but are not limited to, the following compounds (m-i) - (m-xv):
• the photographic coupler compositions according to the present invention are employed in color photographic materials in a manner well known in the color photographic art.
• a supporting substrate is coated with a silver halide emulsion and the coupler composition of the present invention comprising a magenta dye-forming coupler and a hydroxy benzoate compound in an amount sufficient to increase the activity of the dye-forming coupler.
• the photographic material is then imagewise exposed in a manner well known in the color photography art followed by development with an aromatic primary amine developer.
• an aromatic primary amine developer As is well known in the art, the oxidation product of the aromatic primary amine developer reacts with the coupler compound to form the colored dye images.
• compositions and methods of the present invention are demonstrated by the following Examples in which references are to parts by weight unless otherwise specified. Additionally, the following hydroxy benzoate compounds (S-I - S-III) and conventional coupler solvents (S-IV - S-VII) were employed in the Examples:
• Coupler compositions comprising emulsion dispersions of the coupler compound (m-i) as set forth above were prepared using hydroxy benzoate compounds according to the present invention as solvents and using conventional coupler solvents for comparison purposes as set forth in Table I. Specifically, an oil phase was prepared by warming a mixture of 3.4g of coupler compound (m-i), 1.7g of the respective coupler solvent and 10.2g of an auxiliary solvent comprising 2-(2-butoxyethoxy) ethylacetate until dissolution was complete. The weight ratio of coupler compound to the non-auxiliary solvent was 1:0.5.
• the resulting solution was added to an aqueous solution containing 18.13g of a 12.5 weight percent aqueous gelatin, 2.27g of a 10% aqueous Alkanol XC solution and 2.08g of water.
• the resulting mixture was then passed through a colloid mill three times to disperse the oil phase and the resulting dispersion was chilled, noodled and washed for four hours at 40°C to remove the auxiliary solvent.
• the resulting dispersed coupler composition was then coated on a cellulose acetate butyrate support at a level of 1.5 x 10 ⁇ 4 moles/ft2 (108 mg/ft2) together with a sensitized silver bromoiodide emulsion (approximately 0.55 ⁇ , 12% iodide) in the following format: Hardened film strips of the resulting product were exposed (1/25 sec, 1B sensitometer) through a step tablet and then subjected to The Kodak Flexicolor commercial development process. After processing, the status M green densities vs exposure were measured for each film strip using a densitometer. Spectral absorption maxima ( ⁇ max) at densities of approximately 1.0 were measured using a spectrophotometer.
• Coupler compositions comprising emulsion dispersions of the coupler compound (m-ii) as set forth above were prepared using a hydroxy benzoate compound according to the present invention and using conventional coupler solvents for comparison purposes as set forth in Table II. Specifically, an oil phase comprising 0.90g of the coupler compound (m-ii), 0.90g of the respective coupler solvent and 2.70g of the auxiliary solvent described in Example 1 was added to an aqueous phase comprising 7.20g of a 12.5% aqueous gelatin, 0.90g of a 10% aqueous Alkanol XC solution and 2.40g of water. The weight ratio of coupler compound to the non-auxiliary coupler solvent was 1:1.
• Example 1 Hardened film strips of the resulting products were processed in accordance with the methods disclosed in Example 1. Additionally, the gamma values and the ⁇ max values of the processed products were obtained by the procedures set forth in Example 1. The results of these measurements are set forth in Table II.
• coupler compositions comprising emulsion dispersions of coupler compound (m-iii) as set forth above were prepared using a hydroxy benzoate compound according to the present invention and using conventional coupler solvents for comparison purposes as described in Table III.
• the coupler dispersion was coated on the support at a level of 1.0 x 10 ⁇ 4 mole/ft2 together with an equal weight of coupler solvent.
• the resulting film strips were processed in the manner generally described in Example 1 and the respective gamma values were determined.
• the gamma values for the respective solvents are set forth in Table III.
• coupler compositions comprising emulsion dispersions of the polymeric coupler compound (m-v) as set forth above were prepared using a hydroxy benzoate compound according to the present invention and using conventional coupler solvents for comparison purposes as described in Table IV.
• dispersions of the coupler compound were prepared by milling 3.0g of the respective coupler solvent and 1.1g of ethylacetate with 15 ml of a 12.5% aqueous gelatin, 1.9 ml of a 10% aqueous Alkanol XC solution and 9.1 ml of water.
• Each of the respective coupler solvent dispersions were combined with a latex dispersion of the coupler compound (m-v) to provide a weight ratio of coupler compound to solvent of 1:0.5.
• the resulting mixture was stirred for three hours at 40°C to permit loading of the coupler solvent into the latex.
• the coupler solvent-loaded latex dispersions of polymeric coupler compounds (m-v) were coated at a level of 1.5 x 10 ⁇ 4 moles/ft2 together with the silver bromoiodide emulsion described in Example 1 in the following format:
• coupler compositions comprising emulsion dispersions of the polymeric coupler compound (m-vi) as set forth above were prepared using a hydroxy benzoate compound according to the present invention and using conventional coupler solvents for comparison purposes as described in Table V.
• the dispersions were prepared following the procedures described in Example 4.
• the procedures described in Example 4 were also followed in producing hardened film strips.
• the coupler emulsion was coated at a level of 1.0 x 10 ⁇ 4 mole/ft2.
• the processing and measurement procedures described in Example 1 were followed in order to determine the gamma and ⁇ max values.
• the results of the measurements are set forth in Table V. TABLE V Coupler Solvent Gamma ⁇ max S-I 3.50 553 S-IV 2.40 552 S-V 2.42 553 S-VI 3.30 558
• additional coupler compositions comprising emulsion dispersions of the polymeric coupler compound (m-iv) as set forth above were prepared using a hydroxy benzoate compound according to the present invention and using conventional coupler solvents for comparison purposes as described in Table VI.
• Samples of the polymeric coupler compound (m-iv) were prepared using emulsion polymerization techniques or solution polymerization techniques as indicated in Table VI.
• the general procedures of Example 4 were followed in preparing the coupler dispersions and in preparing hardened film strips of the coupler dispersions. Additionally, the hardened strips were then processed and subjected to measurement of Dmax and gamma values in accordance with the procedures of Example 1. The results of these measurements are also set forth in Table VI.
• This invention provides magenta dye-forming coupler compositions with high activity.

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• 1991
  • 1991-12-16 EP EP19910121505 patent/EP0491317A1/de not_active Withdrawn
  • 1991-12-17 JP JP36098391A patent/JPH04294348A/ja active Pending

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