EP0007593B1 - Farbfotografisches Entwicklungsverfahren - Google Patents

Farbfotografisches Entwicklungsverfahren Download PDF

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Publication number
EP0007593B1
EP0007593B1 EP79102564A EP79102564A EP0007593B1 EP 0007593 B1 EP0007593 B1 EP 0007593B1 EP 79102564 A EP79102564 A EP 79102564A EP 79102564 A EP79102564 A EP 79102564A EP 0007593 B1 EP0007593 B1 EP 0007593B1
Authority
EP
European Patent Office
Prior art keywords
hydrophobic
hydrophilic
color
couplers
coupler
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.)
Expired
Application number
EP79102564A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0007593A1 (de
Inventor
Helmut Häseler
Heinz Dr. Meckl
Karl Dr. Lohmer
Willibald Dr. Pelz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0007593A1 publication Critical patent/EP0007593A1/de
Application granted granted Critical
Publication of EP0007593B1 publication Critical patent/EP0007593B1/de
Expired legal-status Critical Current

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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
    • G03C7/32—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.
  • color photographic images by chromogenic development, i.e. by developing imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - the oxidation product of the developer substances resulting in accordance with the silver image reacting with the color coupler to form a dye image.
  • color developers i.e. by developing imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - the oxidation product of the developer substances resulting in accordance with the silver image reacting with the color coupler to form a dye image.
  • Aromatic compounds containing primary amino groups in particular those of the p-phenylenediamine type, are usually used as color developers.
  • 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.
  • hydrophobic couplers from organic solutions are expediently incorporated into the casting solution for the photographic layers in the presence of high-boiling solvents which are immiscible or only miscible with water.
  • hydrophobic color developer compounds are particularly suitable for this.
  • the corresponding color couplers should also be emulsified in hydrophobic form.
  • the hydrophobic or in hydrophobic emulsified form yellow couplers now often have the disadvantage that the dye formation during development proceeds more slowly than with a hydrophilic yellow coupler with a hydrophilic developer substance, especially when the yellow developing layer is at the bottom of the layer package. In this regard, they are superior to hydrophilic yellow couplers, which, however, 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 (for example DE-A-1 962 606, DE-B-1 547 816, GB- A-1 107 453, US-A-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 has for its object a process for the chromogenic development of a color photographic material with at least three silver halide emulsion layers different Specify spectral sensitivity and color couplers assigned to them, at least one color coupler being hydrophobic and at least one further color coupler being hydrophilic, in which sufficiently high color densities are achieved both from hydrophobic and from hydrophilic color couplers.
  • a blue-green partial color image with good tropical resistance and a yellow partial color image with good lightfastness are to be obtained simultaneously in the chromogenic development.
  • the solution to the problem is that 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 light fastness if the color photographic material is both a cyan coupler emulsified with a hydrophobic oil former and a hydrophilic one without the use of an oil former contains incorporated yellow coupler. A hydrophobic yellow coupler emulsified using a comparatively hydrophilic oil former also acts in the same way as a hydrophilic yellow coupler.
  • the color developer preparation used for development accordingly contains at least a first (hydrophilic) and a second (hydrophobic) color developer compound.
  • 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 mainly reacts with the hydrophilic coupler.
  • R 3 preferably denotes sulfoalkyl, carboxyalkyl or hydroxyalkyl and in the case of the second (hydrophobic) color developer compound R 3 preferably denotes alkoxyalkyl, alkyl or methylsufonamidoalkyl.
  • 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, i.e. at 20 ° C, they are generally liquid or they melt at relatively low temperatures, i.e. 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. 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 into which they are incorporated.
  • they should also be colorless, stable to light, heat and moisture and should also be inert to the various development and treatment baths in which the color photographic material is developed.
  • 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 sense 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 layer support, 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.
  • the blue-sensitive silver halide emulsion layer is assigned a yellow coupler
  • the green-sensitive silver halide emulsion layer is a magenta coupler
  • the red-sensitive silver halide emulsion layer is a cyan coupler.
  • Associated is understood to mean that the mutual arrangement of the silver halide emulsion layer and the color coupler is of such a type that an interaction between them is possible which allows an imagewise correspondence between the silver image formed and the imagewise distribution of the image dye produced in the chromogenic development
  • Color couplers are embedded in the light-sensitive silver halide emulsion layer itself, but can also be contained in a non-light-sensitive neighboring layer, since the developer oxidation products generated during color development should only react with the assigned color coupler and should not diffuse into unassigned color coupler-containing layers if possible
  • Photosensitive silver halide emulsion layers still contain separating layers, which may consist of pure binder or may contain substances distributed in a binder that can react with color developer oxidation products to form colorless substances. In a known manner, 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.
  • Teal couplers are, for example, derivatives of phenol which, in the 4-position, can react with oxidized color developers to give cyan indochinone dyes.
  • Pyrazolone derivatives should be mentioned in particular as purple couplers, and derivatives of benzoylacetanilide or pivaloylacetanilide are generally used as yellow couplers.
  • Hydrophobic color couplers are those that generally cannot 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 "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 optionally be hydrophobic or hydrophilic or even be 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 substrate contains the coupler for producing the yellow image in the blue-sensitive underlayer, the coupler 2 for producing the purple image in the green-sensitized middle layer and the coupler 3 for producing the blue-green in the red-sensitized top layer Picture.
  • Coupler and coupler3 are emulsified using the hydrophilic oil former E. The formulas of the couplers are given at the end of the examples.
  • the material is exposed behind a silver gray wedge and processed as follows: developer, 35 ° C, 2 min.
  • Example 1 The material of Example 1 is in the following developer at 35 ° C and 2 min. processed: 1 liter contains:
  • Example 3 The material of Example 3 is processed as indicated in Example 2.
  • Example 6 The material of Example 6 is developed in the following developer:
  • 1 liter contains: Further processing as indicated in Example 6.
  • 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 hydrophobic embedded couplers reacted.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP79102564A 1978-08-01 1979-07-20 Farbfotografisches Entwicklungsverfahren Expired EP0007593B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2833655 1978-08-01
DE19782833655 DE2833655A1 (de) 1978-08-01 1978-08-01 Farbfotografisches entwicklungsverfahren

Publications (2)

Publication Number Publication Date
EP0007593A1 EP0007593A1 (de) 1980-02-06
EP0007593B1 true EP0007593B1 (de) 1981-01-21

Family

ID=6045915

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79102564A Expired EP0007593B1 (de) 1978-08-01 1979-07-20 Farbfotografisches Entwicklungsverfahren

Country Status (4)

Country Link
US (1) US4297438A (enrdf_load_stackoverflow)
EP (1) EP0007593B1 (enrdf_load_stackoverflow)
JP (1) JPS5521097A (enrdf_load_stackoverflow)
DE (2) DE2833655A1 (enrdf_load_stackoverflow)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2613120C2 (de) * 1976-03-27 1984-05-17 Agfa-Gevaert Ag, 5090 Leverkusen Wäßriger alkalischer Farbenentwickler und Verfahren zur Entwicklung von farbphotographischen Bildern
DE3130079A1 (de) * 1981-07-30 1983-02-17 Agfa-Gevaert Ag, 5090 Leverkusen Farbfotografisches aufzeichnungsmaterial
JPS58147743A (ja) * 1982-02-25 1983-09-02 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料
FR2554935A1 (fr) * 1983-11-15 1985-05-17 Kis France Sa Composition pour reveler les photographies en couleurs
US4882264A (en) * 1984-01-20 1989-11-21 Olin Hunt Specialty Products Inc. Color developer composition
DE3681305D1 (de) * 1985-02-16 1991-10-17 Konishiroku Photo Ind Lichtempfindliches photographisches material.
US5194348A (en) * 1986-08-05 1993-03-16 Fuji Photo Film Co., Ltd. Color photographs and method for preparation of the same
JPS63110453A (ja) * 1986-10-29 1988-05-14 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPH02133119U (enrdf_load_stackoverflow) * 1989-04-05 1990-11-05
JPH04199915A (ja) * 1990-11-29 1992-07-21 Kokusai Electric Co Ltd 自動送信電力制御回路

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2241769A (en) * 1939-03-29 1941-05-13 Eastman Kodak Co Sulphonic acid derivatives of aryl diamines
BE490160A (enrdf_load_stackoverflow) * 1948-07-15
DE954311C (de) * 1953-12-06 1956-12-13 Agfa Ag Verfahren zur Herstellung von farbigen Bildern durch chromogene Entwicklung
DE1127714B (de) * 1960-08-20 1962-04-12 Perutz Photowerke G M B H Verfahren zur Herstellung von farbphotographischen Halogensilberemulsionen
FR1299899A (fr) * 1960-09-09 1962-07-27 Agfa Ag Procédé de développement d'images photographiques, notamment d'images en couleurs, à l'aide de dérivés de p-dialkylamino aniline
US3515557A (en) * 1965-04-12 1970-06-02 Du Pont Photographic color film and process of making same
US3859095A (en) * 1969-12-13 1975-01-07 Agfa Gevaert Ag Color-photographic material with improved color reproduction
GB1365300A (en) * 1970-12-01 1974-08-29 Agfa Gevaert Colour development of photographic silver halide elements
US3656950A (en) * 1970-12-03 1972-04-18 Eastman Kodak Co Color photographic processes
US3658525A (en) * 1970-12-03 1972-04-25 Eastman Kodak Co Reversal color photographic processes
JPS6213658B2 (enrdf_load_stackoverflow) * 1974-05-23 1987-03-27 Fuji Photo Film Co Ltd
DE2613120C2 (de) * 1976-03-27 1984-05-17 Agfa-Gevaert Ag, 5090 Leverkusen Wäßriger alkalischer Farbenentwickler und Verfahren zur Entwicklung von farbphotographischen Bildern
JPS532779A (en) * 1976-06-30 1978-01-11 Matsushita Electric Works Ltd Method of cutting synthetic resin sheet at fixed position

Also Published As

Publication number Publication date
JPS5521097A (en) 1980-02-14
EP0007593A1 (de) 1980-02-06
DE2833655A1 (de) 1980-02-21
US4297438A (en) 1981-10-27
JPS6316731B2 (enrdf_load_stackoverflow) 1988-04-11
DE2960087D1 (en) 1981-03-12

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