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
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/30—Developers
• • 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
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers

Definitions

• the invention relates to a color photographic development process in which a color photographic material containing a hydrophobic cyan coupler and a hydrophilic yellow coupler is developed with a mixture of a hydrophobic and a hydrophilic color developer.
• the blue-green dyes produced by chromogenic development show poor resistance to the action of light if the underlying blue-green couplers belong to the class of naphthol derivatives.
• dyes from cyan couplers based on phenol are sufficiently lightfast.
• the dyes formed from these couplers are generally particularly susceptible to tropical conditions if the couplers are water- or alkali-soluble and, consequently, without the use of hydrophobic coupler solvents, so-called oil formers, in the casting solutions for the red-sensitive silver halide emulsion layer or in adjacent, non-light-sensitive binder layer have been incorporated.
• the cyan dyes behave somewhat more favorably if the hydrophobic oil formers mentioned are used to incorporate the underlying color couplers.
• the hydrophobic couplers of organic solutions are incorporated with water does not or only to a small extent miscible solvents in the casting solution for the photographic layers B ekannkanntlich advantageously in the presence of high-boiling.
• An emulsified fine droplet of a solution of the coupler in the oily coupler solvent is obtained in which the coupler is distributed in the hydrophilic binder, protected by an oily shell, as it were.
• the yellow couplers which are hydrophobic or in a hydrophobically emulsified form, now often have the disadvantage that the development of dyes proceeds more slowly than in the case of a hydrophilic one Yellow coupler with a hydrophilic developer substance, especially when the yellow developing layer is at the bottom of the layer package.
• hydrophilic yellow couplers are superior to them, but they do not give the desired high color density with the hydrophobic color developer substances and often form dyes whose light fastness is unsatisfactory.
• color couplers emulsified in hydrophobic form in addition to water- or alkali-soluble color couplers in the same material, possibly even in the same layer, is known per se (e.g. DE-OS 1 962 606, DE - AS 1 5 47 816, GB Patent 1,107,453. U.S. Patent 3,515,557). This is used, for example, to adapt the reactivity of different color couplers to one another. As stated above, the color developer substance used for the development of such materials does not lead equally to the desired high maximum color density in hydrophobic and hydrophilic color couplers.
• the invention is based on the object of specifying a method for the chromogenic development of a color photographic material with at least three silver halide emulsion layers of different spectral sensitivity and color couplers associated therewith, at least one color coupler being hydrophobic and at least one further color coupler being hydrophilic, in which both hydrophobic and hydrophilic color couplers are sufficiently high color densities can be achieved.
• the; chromogenic development both a blue-green partial color image with good tropical resistance and a yellow partial color image with good light fastness can be obtained simultaneously.
• a developer composition is used for the chromogenic development of the material described, which contains both a hydrophobic and a hydrophilic color developer compound. Sufficiently high color densities are achieved both from the hydrophobic color couplers and from the hydrophilic color couplers. It has also been found that this method can simultaneously obtain both a blue-green partial color image with good tropical resistance and a yellow partial color image with good lightfastness if the color photographic material is both a cyan coupler emulsified with a hydrophobic ulcer and a hydrophilic one without the use of an oil former contains incorporated yellow coupler. In the same way as a hydrophilic yellow coupler, a hydrophobic yellow coupler which is eumulsified using a comparatively hydrophilic oil former also acts.
• the color developer preparation used for development accordingly contains at least two color developer compounds of different hydrophilicity.
• the difference in hydrophilicity results in a different distribution of the color developer oxidation products in the two-phase system consisting of hydrophilic binder and hydrophobic oil former.
• the hydrophobic color developer compound (in oxidized form) penetrates the oil droplets of the coupler solvent much more easily and therefore reacts preferentially with the hydrophobic coupler, while the hydrophilic color developer compound remaining mainly in the aqueous phase reacts predominantly with the hydrophilic coupler.
• hydrophilic couplers also include hydrophobic couplers per se, which are dissolved in hydrophilic oil formers and are thus dispersed in the layer.
• hydrophobic-hydrophilic in the characterization of the color developer compounds in the sense of the invention, it is therefore only important that two color developer compounds are used which lead to a different distribution of the developer oxidation products in the two-phase system.
• a hydrophilic color developer compound in which R 3 is a sulfoalkyl group can be combined with a hydrophobic color developer compound in which R 3 is an alkoxyalkyl group.
• the more hydrophilic the one and the more hydrophobic the other of the two color developer compounds the more favorable a result can be achieved.
• the quantitative ratio between the hydrophilic and hydrophobic color developer compound can be varied within wide limits according to the respective requirements, for example between 1: 6 and 6: 1 (parts by weight).
• the person skilled in the art can determine the most favorable quantity ratio by means of a simple routine test.
• Oil formers for the purposes of the present invention are the known coupler solvents which are insoluble or only slightly soluble in water, which are sometimes referred to in the literature as crystalloid solvents and have been described, for example, in US Pat. Nos. 2,304,940 and 2,322,027.
• the oil formers can be hydrophobic or hydrophilic; at least in the neutral or acidic medium, they form their own second phase in addition to the hydrophilic binder phase.
• Hydrophilic oil formers are known from US Pat. Nos. 3,689,271, 3,764,336 and 3,765,897. These are high-boiling organic low-molecular compounds which can penetrate semipermeable membranes and which generally boil above 175 ° C. At room temperature, ie at 20 ° C, they are generally liquid or they melt at relatively low temperatures, ie at temperatures below 100 ° C. They are referred to as oil formers because they generally form oily or liquid solutions when mixed with couplers.
• Coupler solvents are e.g.
• couplers those compounds which have one or more polar groups or atoms, for example hydroxyl, carboxylic acid, amide or keto groups or halogen atoms.
• the dissolving effect on the couplers should be as high as possible, and of course the solvents should be inert towards the silver halide emulsion in which they are incorporated. Of course, they should also be colorless if possible. heat and moisture stable and also be inert towards the various development and treatment baths in which the color photographic material is developed. In addition, their volatility should be as low as possible.
• Oil formers which are used particularly frequently and which have also proven to be outstandingly suitable in the context of the present invention are, for example, phosphoric acid triaryl esters, in particular tricresyl phosphate, and phthalic acid dialkyl esters, such as di-n-butyl phthalate.
• the list contains a whole series of compounds which, owing to the different functional groups, behave differently in terms of their affinity for the couplers to be dissolved and for the reagents of the various photographic treatment baths, in particular the developer oxidation product.
• the photographic material to be developed according to the method of the invention contains at least three silver halide emulsion layers with different spectral sensitivity on a conventional substrate which can be transparent but is preferably opaque.
• a non-diffusing color coupler is assigned to each of these three layers in order to produce a partial color image, the color of which is generally complementary to the color of the light, for which the assigned silver halide emulsion layer is predominantly sensitive.
• a yellow coupler is assigned to the blue-sensitive silver halide emulsion layer, a purple coupler to the green-sensitive silver halide emulsion layer and a cyan coupler to the red-sensitive silver halide emulsion layer.
• Associated is understood to mean that the mutual arrangement of the silver halide emulsion layer and color coupler is of such a type that an interaction between them is possible which permits an imagewise match between the silver image formed and the imagewise distribution of the image dye produced in the chromogenic development.
• the color coupler is usually embedded in the light-sensitive silver halide emulsion layer itself; however, it can also be contained in a non-light-sensitive neighboring layer for this purpose.
• the developer oxidation products generated during color development should only react with the assigned color coupler and if possible not in unassigned colors coupler-containing layers are to be diffused, expediently there are still separating layers between the light-sensitive silver halide emulsion layers, which may consist of pure binder or may contain substances distributed in a binder which are capable of reacting with color developer oxidation products to form colorless substances.
• these can be white coupler compounds or non-diffusing hydroquinone derivatives.
• the preferred hydrophilic binder in the process of the present invention is gelatin, but it can also be replaced in whole or in part by other natural or synthetic binders. In the two-phase system mentioned, the hydrophilic binder represents the hydrophilic phase.
• Pyrazolone derivatives should be mentioned in particular, and derivatives of benzoylacetanilide or pivaloylacetanilide are generally used as yellow couplers.
• Hydrophobic color couplers are those that can generally not be incorporated into the casting solutions for the photographic layers from aqueous alkaline solutions. Groups which render water or alkali soluble, in particular sulfo or carboxyl groups, are generally absent from the hydrophobic color couplers. Conversely, the hydrophilic color couplers normally contain at least one sulfo or carboxyl group which makes them soluble in aqueous alkali. Because of this latter property, the hydrophilic color couplers are sometimes referred to as "soluble" couplers, in contrast to the "insoluble" or hydrophobic couplers.
• the color photographic material to be developed contains at least one hydrophobic color coupler emulsified in droplets of a more or less hydrophobic oil former and at least one hydrophilic color coupler, which may have been added to the layer in the form of an aqueous alkaline solution or in the form of a Emulsions in a hydrophilic oil former.
• Hydrophobic and hydrophilic color couplers can be contained in the same layer or in different layers. In the first case, both couplers can contribute to the generation of the same partial color image.
• the cyan coupler is hydrophobic and the yellow coupler is hydrophilic.
• the magenta coupler can be either hydrophobic or hydrophilic, or even as a combination of a hydrophilic magenta coupler with a magenta coupler emulsified in hydrophobic form.
• a color photographic material with three gelatin-silver halide emulsion layers applied to an opaque support contains the coupler 1 for the generation of the yellow image in the blue-sensitive underlayer, the coupler 2 for the generation of the purple image in the green-sensitized middle layer and the coupler 3 for the generation of the in the red-sensitized top layer teal image.
• Coupler 2 and coupler 3 are emulsified using the hydrophilic oil former E. The formulas of the couplers are given at the end of the examples.
• Example 1 The material is as described in Example 1. In contrast to this, coupler 3 is dissolved in dibutyl phthalate (hydrophobic) and this solution is dispersed in the top layer. The same applies to coupler 4 (instead of coupler 1) in the lower layer. The development is carried out as in Example 1.
• Example 3 The material of Example 3 is processed as indicated in Example 2.
• Example 1 The material is as described in Example 1. In contrast to this, coupler 3 is dissolved in dibutyl phthalate and this solution is dispersed in the top layer. Otherwise, the material has the structure described in Example 1. Development takes place with the following developer at 35 ° C. and 2 minutes:
• the wedge images obtained according to Examples 6 to 8 are evaluated in the same way as the wedge images of Examples 1 to 5.
• the result of these measurements is summarized in Table 2.
• the table shows that an optimal result is obtained if a color photographic material with both hydrophilically and hydrophobically incorporated couplers is processed with a developer composition which contains two developer substances, one of which preferably reacts with hydrophilically incorporated couplers and the other preferably with hydrophobically incorporated couplers responds.

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

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• 1978
  • 1978-08-01 DE DE19782833655 patent/DE2833655A1/de not_active Withdrawn
• 1979
  • 1979-07-20 EP EP79102564A patent/EP0007593B1/fr not_active Expired
  • 1979-07-20 DE DE7979102564T patent/DE2960087D1/de not_active Expired
  • 1979-07-27 US US06/061,472 patent/US4297438A/en not_active Expired - Lifetime
  • 1979-07-31 JP JP9688279A patent/JPS5521097A/ja active Granted

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