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WO1991003005A1 - Method of photographic processing - Google Patents

Method of photographic processing Download PDF

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Publication number
WO1991003005A1
WO1991003005A1 PCT/EP1990/001314 EP9001314W WO9103005A1 WO 1991003005 A1 WO1991003005 A1 WO 1991003005A1 EP 9001314 W EP9001314 W EP 9001314W WO 9103005 A1 WO9103005 A1 WO 9103005A1
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WO
WIPO (PCT)
Prior art keywords
swell
processing
layer
solution
components
Prior art date
Application number
PCT/EP1990/001314
Other languages
French (fr)
Inventor
John Richard Fyson
Original Assignee
Kodak Limited
Eastman Kodak Company
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 Kodak Limited, Eastman Kodak Company filed Critical Kodak Limited
Priority to AT90913132T priority Critical patent/ATE89422T1/en
Publication of WO1991003005A1 publication Critical patent/WO1991003005A1/en

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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
    • G03C7/3017—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction
    • G03C7/302—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction using peroxides
    • 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
    • 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
    • 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

Definitions

  • METHOD OF PHOTOGRAPHIC PROCESSING This invention relates to a method of processing a photographic silver halide material.
  • an imagewise exposed photographic silver halide material is processed in one or more aqueous processing solutions.
  • a negative colour image is formed in a film and a colour print is made by exposing a colour negative paper to the negative image.
  • the paper is then processed in a colour developer to form a silver image and corresponding dye image in each of three colour layers thus together forming the desired full colour image.
  • a typical second processing stage is a bleach-fix solution which bleaches the unwanted silver image and removes undeveloped silver halide.
  • Photographic materials not containing silver halide layers are also known which are neverthless processed with solutions.
  • the processing steps are usually accomplished by immersing the photographic material in the processing solutions, often in a processing machine, for a particular length of time at a particular temperature.
  • time and temperature determines the extent of the processing.
  • the time and temperature have to be accurately controlled.
  • the present invention provides a method of controlling the amount of processing solution components entering the layer or layers of a photographic material hence controlling the processing itself by novel means.
  • a method of processing a photographic material comprising a support bearing at least one swellable layer which method comprises contacting the material with a processing solution containing a component which limits the swell of the layer so that its ta e—up of processing solution components is controlled by the degree of said swell.
  • the photographic material may be a black—and—white or colour material and may contain a photosensitive silver halide layer comprising a hydrophilic colloid binder, eg gelatin, a gelatin derivative or polyvinyl alcohol.
  • a hydrophilic colloid binder eg gelatin, a gelatin derivative or polyvinyl alcohol.
  • Non-hydrophilic binders may also be used especially in non—silver halide systems.
  • the material may be one for use in physically developed systems including both photosensitive and non—photosensitive materials, for example, materials for the silver salt diffusion transfer process.
  • the material may be for the diazo, dye transfer or dye bleach process.
  • the solution containing the swell limiting compound is preferably aqueous but this is not essential.
  • Non—aqueous solutions for example comprising an alcohol, glycol, glycol ether or hydrocarbon solvents may also be employed.
  • the photographic material is successively contacted with a number of processing solutions each one containing swell—limiting components in such amounts that the swell of the layer is increased with each solution so that further processing solution components are successively taken up by said layer.
  • the present invention provides a controlled way of processing photographic products using small amounts of liquid. Processing times can be shortened as concentrations can be higher. More even processing can be achieved for surface applied solutions and processing normally undertaken above room temperature in a deep tank can be achieved at room temperature itself.
  • the component that limits the swell of the emulsion layer may be a salt, particularly an alkali metal or ammonium salt.
  • Such salts may be chlorides, sulphates or carbonates. Examples of particular salts are sodium chloride, potassium sulphate, potassium carbonate, ammonium sulphate, etc.
  • the salt is chosen so as not to interfere with the processing function. Hence, for developers, potassium carbonate or sulphate would be suitable.
  • the developing agent is added separately this could be from an acid solution while the remainder of the necessary components could be added subsequently with sufficient alkali to provide the desired pH for processing.
  • the processing solutions may contain a thickener and hence be viscous, such solutions being suitable for surface application.
  • the processing solution may contain any of the many components used in photography, for example as described in "Modern Photographic Processing” by Grant M. Haist, John Wiley and Sons, 1979.
  • the processing solution may be an amplification solution containing a colour developing agent and a redox amplification oxidant, e.g. a peroxide, periodate or cobalt (III) complex as described in US Patents 3 674 490 or 3 862 842. In such a case it is convenient to keep and apply the developing agent and the oxidant in separate solutions as a solution of them both is unstable.
  • the photographic material to be processed may be of many different kinds and contain a variety of additives as described in Research Disclosure Item 17643 December 1978 pages 22-31, Kenneth Mason Publications, Havant, Hampshire, UK.
  • silver halide emulsion layers comprise gelatin as binder which is hardened to a conventional extent. Such a hardened layer is however still able to swell in aqueous solutions.
  • Other binders and polymers may also be present as described in the Research Disclosure article cited above. The following examples are given for a better understanding of the invention. All processing was carried out at 20°C.
  • Example 1 Conventional Colour Processing
  • the density of the yellow Dmax (blue sensitive) area was used to measure the extent of development in a two stage process.
  • samples of a colour negative paper comprising pure silver chloride emulsions were used.
  • the paper was dipped into a test base solution (see table below for composition) for 20 seconds to allow the paper's gelatin layers to swell to their maximum extent (this was established using a swellmeter).
  • the potassium carbonate is present to control the swell of the paper gelatin in the base solution.
  • solution 1 the density is inferior to the experiment with carbonate and hydroxide (solution 2). The results also indicate that the presence of carbonate gives a more even result. Solution 3 was used to demonstrate that extra base contributed by the carbonate was not responsible for all the density gain shown by solution 2.
  • a negative colour paper which contained a low silver coating weight (as silver chloride) was used.
  • the paper was then dipped into a third solution containing 50 mls/1 30% hydrogen peroxide for 3 seconds before blotting for the last time.
  • the sample was allowed to stand for 30 seconds (again the reaction appeared complete in 5 seconds) before washing in water for 3 minutes and then drying at room temperature.
  • the sample was read at 10 random points, using a Macbeth densitometer, with a blue status A filter in the reflection head. From the 10 readings a mean and standard deviation (a measure of the evenness of the process) were calculated.

Landscapes

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

Abstract

A method of processing a photographic material comprising a support bearing at least one swellable layer which method comprises contacting the material with a processing solution containing a component which limits the swell of the layer so that its take-up of processing solution components is controlled by the degree of said swell.

Description

METHOD OF PHOTOGRAPHIC PROCESSING This invention relates to a method of processing a photographic silver halide material. In order to produce a visible image, an imagewise exposed photographic silver halide material is processed in one or more aqueous processing solutions. In one form of colour photography a negative colour image is formed in a film and a colour print is made by exposing a colour negative paper to the negative image. The paper is then processed in a colour developer to form a silver image and corresponding dye image in each of three colour layers thus together forming the desired full colour image. A typical second processing stage is a bleach-fix solution which bleaches the unwanted silver image and removes undeveloped silver halide. Photographic materials not containing silver halide layers are also known which are neverthless processed with solutions. The processing steps are usually accomplished by immersing the photographic material in the processing solutions, often in a processing machine, for a particular length of time at a particular temperature. Thus it is the combination of time and temperature which determines the extent of the processing. In the development stage in particular, the time and temperature have to be accurately controlled.
The present invention provides a method of controlling the amount of processing solution components entering the layer or layers of a photographic material hence controlling the processing itself by novel means.
According to the present invention there is provided a method of processing a photographic material comprising a support bearing at least one swellable layer which method comprises contacting the material with a processing solution containing a component which limits the swell of the layer so that its ta e—up of processing solution components is controlled by the degree of said swell.
The photographic material may be a black—and—white or colour material and may contain a photosensitive silver halide layer comprising a hydrophilic colloid binder, eg gelatin, a gelatin derivative or polyvinyl alcohol. Non-hydrophilic binders may also be used especially in non—silver halide systems. The material may be one for use in physically developed systems including both photosensitive and non—photosensitive materials, for example, materials for the silver salt diffusion transfer process. In addition the material may be for the diazo, dye transfer or dye bleach process.
The solution containing the swell limiting compound is preferably aqueous but this is not essential. Non—aqueous solutions, for example comprising an alcohol, glycol, glycol ether or hydrocarbon solvents may also be employed.
In a particular preferred embodiment the photographic material is successively contacted with a number of processing solutions each one containing swell—limiting components in such amounts that the swell of the layer is increased with each solution so that further processing solution components are successively taken up by said layer. This enables the components needed by, say, a developer to be added to an emulsion layer separately or in groups.
The present invention provides a controlled way of processing photographic products using small amounts of liquid. Processing times can be shortened as concentrations can be higher. More even processing can be achieved for surface applied solutions and processing normally undertaken above room temperature in a deep tank can be achieved at room temperature itself.
In addition, since the components can be added sequentially, the final combination and concentration of components may be impossible to obtain in the conventional way. For example the concentration of a component could be higher than could be achieved from a conventional, stable developer formulation or the particular combination might be one that would be unstable if combined in a single solution. The component that limits the swell of the emulsion layer may be a salt, particularly an alkali metal or ammonium salt. Such salts may be chlorides, sulphates or carbonates. Examples of particular salts are sodium chloride, potassium sulphate, potassium carbonate, ammonium sulphate, etc. Preferably the salt is chosen so as not to interfere with the processing function. Hence, for developers, potassium carbonate or sulphate would be suitable.
If the developing agent is added separately this could be from an acid solution while the remainder of the necessary components could be added subsequently with sufficient alkali to provide the desired pH for processing.
The processing solutions may contain a thickener and hence be viscous, such solutions being suitable for surface application.
The processing solution may contain any of the many components used in photography, for example as described in "Modern Photographic Processing" by Grant M. Haist, John Wiley and Sons, 1979. The processing solution may be an amplification solution containing a colour developing agent and a redox amplification oxidant, e.g. a peroxide, periodate or cobalt (III) complex as described in US Patents 3 674 490 or 3 862 842. In such a case it is convenient to keep and apply the developing agent and the oxidant in separate solutions as a solution of them both is unstable.
The photographic material to be processed may be of many different kinds and contain a variety of additives as described in Research Disclosure Item 17643 December 1978 pages 22-31, Kenneth Mason Publications, Havant, Hampshire, UK. As is customary, silver halide emulsion layers comprise gelatin as binder which is hardened to a conventional extent. Such a hardened layer is however still able to swell in aqueous solutions. Other binders and polymers may also be present as described in the Research Disclosure article cited above. The following examples are given for a better understanding of the invention. All processing was carried out at 20°C. Example 1 — Conventional Colour Processing
In order to demonstrate the invention, the density of the yellow Dmax (blue sensitive) area was used to measure the extent of development in a two stage process. For conventional processing, samples of a colour negative paper comprising pure silver chloride emulsions were used. To process these, the paper was dipped into a test base solution (see table below for composition) for 20 seconds to allow the paper's gelatin layers to swell to their maximum extent (this was established using a swellmeter). The paper was then blotted using photographic blotting paper then plunged into a 20g/l solution of 4-N-ethyl—N-(β-Methanesulphonamidoeth l—o-toluidine sesquisulphate (CD3) for 3 seconds, before removing and blotting again. The sample was allowed to stand for 30 seconds (although the reaction appeared complete in 5 seconds) before washing in water for 3 minutes and then drying at room temperature. The sample was read at 10 random points, using a Macbeth densitometer, with a blue status A filter in the reflection head. From the 10 readings a mean and standard deviation (a measure of the evenness of the process) were calculated. Base Solutions
Soln 1 Soln 2 Soln 3 NaOH 20g/l 20g/l
K2C03 anhydrous - lOOg/l lOOg/l
Figure imgf000007_0001
The potassium carbonate is present to control the swell of the paper gelatin in the base solution.
Swell measurements indicate that this restricts the swell of the the material to 12 microns, whereas in water it was 17.5 microns and in 20g/l sodium hydroxide, 21 microns. The results above demonstrate the action of the carbonate. Without the carbonate
(solution 1) the density is inferior to the experiment with carbonate and hydroxide (solution 2). The results also indicate that the presence of carbonate gives a more even result. Solution 3 was used to demonstrate that extra base contributed by the carbonate was not responsible for all the density gain shown by solution 2.
Example 2 — Redox Amplification Processing
A negative colour paper which contained a low silver coating weight (as silver chloride) was used.
2 This has silver coating weights of lOmg/m , lOmg/m 2 and 40mg/m2 in the red, green and blue layers respectively. The dispersions were similar to those used in the paper of Example 1 and were coated at the same laydown. To process these, the paper was dipped into a test 'base solution' (same as for the previous example) for 20 seconds to allow the paper's gelatin layers to swell to its maximum extent. The paper was then blotted using photographic blotting paper then plunged into a 20g/l CD3 solution to which lOOg/l anhydrous sodium sulphate had been added, for 3 seconds, before removing and blotting again. The paper was then dipped into a third solution containing 50 mls/1 30% hydrogen peroxide for 3 seconds before blotting for the last time. The sample was allowed to stand for 30 seconds (again the reaction appeared complete in 5 seconds) before washing in water for 3 minutes and then drying at room temperature. The sample was read at 10 random points, using a Macbeth densitometer, with a blue status A filter in the reflection head. From the 10 readings a mean and standard deviation (a measure of the evenness of the process) were calculated.
Results:
Figure imgf000008_0001
Again the addition of the carbonate as a swell control agent in the first bath gave the coating space to expand in the second solution and therefore take up more developing agent than with conventional solutions, thus giving greater density. Further expansion was possible in the third solution because of the sodium sulphate added to the second bath, the CD3 solution.
In practice, if these three solutions had been mixed together they would have rapidly degraded. An experiment indicated that if the three solutions are mixed in equal proportions a black tar begins to form after 30 seconds. In the imbibed process no tarring was observed in the paper samples.

Claims

1. A method of processing a photographic material comprising a support bearing at least one swellable layer which method comprises contacting the material with a processing solution containing a component which limits the swell of the layer so that its take—up of processing solution components is controlled by the degree of said swell.
2. A method as claimed in Claim 1 in which the photographic material is successively contacted with a number of processing solutions each one containing swell-limiting components in such amounts that the swell of the emulsion layer is increased with each solution so that further processing solution components are successively taken up by said layer.
3. A method as claimed in claim 1 or 2 in which the swell-limiting compound is an alkali metal or ammonium water—soluble salt.
4. A method as claimed in claim 3 in which the salt is a chloride, sulphate or carbonate.
5. A method as claimed in any of claims 1—4 in which the solution is aqueous.
6. A method as claimed in any of claims 1-5 in which the swellable layer is a photosensitive silver halide emulsion layer.
7. A method as claimed in any of claims 1—6 in which the swellable layer comprises a hydrophilic colloid binder.
8. A method as claimed in any of claims 1—7 in which the photographic material is a multilayer colour material.
PCT/EP1990/001314 1989-08-16 1990-08-09 Method of photographic processing WO1991003005A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90913132T ATE89422T1 (en) 1989-08-16 1990-08-09 PROCEDURE FOR PHOTOGRAPHIC TREATMENT.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8918723.1 1989-08-16
GB898918723A GB8918723D0 (en) 1989-08-16 1989-08-16 Method of photographic processing

Publications (1)

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WO1991003005A1 true WO1991003005A1 (en) 1991-03-07

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PCT/EP1990/001314 WO1991003005A1 (en) 1989-08-16 1990-08-09 Method of photographic processing

Country Status (5)

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EP (1) EP0487616B1 (en)
JP (1) JP2690396B2 (en)
DE (1) DE69001610T2 (en)
GB (1) GB8918723D0 (en)
WO (1) WO1991003005A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1979001020A1 (en) * 1978-05-02 1979-11-29 Polaroid Corp Photosensitive elements
US4347301A (en) * 1980-11-26 1982-08-31 Polaroid Corporation Novel diffusion transfer film units
US4374922A (en) * 1980-07-11 1983-02-22 Konishiroku Photo Industry Co., Ltd. Method for the formation of a dye image
US4569898A (en) * 1984-11-23 1986-02-11 Polaroid Corporation Photographic film unit with protective, limited swell polymer for silver halide grains
US4626494A (en) * 1984-08-15 1986-12-02 Fuji Photo Film Co., Ltd. Hardened color diffusion transfer photographic materials

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5054330A (en) * 1973-09-10 1975-05-14
JPS51101530A (en) * 1975-03-05 1976-09-08 Fuji Photo Film Co Ltd
JPS54111827A (en) * 1978-02-21 1979-09-01 Konishiroku Photo Ind Co Ltd Processing method for silver halide color photographic material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1979001020A1 (en) * 1978-05-02 1979-11-29 Polaroid Corp Photosensitive elements
US4374922A (en) * 1980-07-11 1983-02-22 Konishiroku Photo Industry Co., Ltd. Method for the formation of a dye image
US4347301A (en) * 1980-11-26 1982-08-31 Polaroid Corporation Novel diffusion transfer film units
US4626494A (en) * 1984-08-15 1986-12-02 Fuji Photo Film Co., Ltd. Hardened color diffusion transfer photographic materials
US4569898A (en) * 1984-11-23 1986-02-11 Polaroid Corporation Photographic film unit with protective, limited swell polymer for silver halide grains

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DERWENT'S ABSTRACT, No. 03213C/02; & SU,A,658 520, Publ. Week 8002. *

Also Published As

Publication number Publication date
JP2690396B2 (en) 1997-12-10
EP0487616B1 (en) 1993-05-12
JPH04507306A (en) 1992-12-17
DE69001610T2 (en) 1993-12-09
EP0487616A1 (en) 1992-06-03
DE69001610D1 (en) 1993-06-17
GB8918723D0 (en) 1989-09-27

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