EP0561860A1 - Method of photographic silver halide processing, silver halide materials and solutions therefor. - Google Patents
Method of photographic silver halide processing, silver halide materials and solutions therefor.Info
- Publication number
- EP0561860A1 EP0561860A1 EP92900247A EP92900247A EP0561860A1 EP 0561860 A1 EP0561860 A1 EP 0561860A1 EP 92900247 A EP92900247 A EP 92900247A EP 92900247 A EP92900247 A EP 92900247A EP 0561860 A1 EP0561860 A1 EP 0561860A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- hydrogen
- black
- silver halide
- colour
- 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.)
- Granted
Links
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
- G03C7/407—Development processes or agents therefor
- G03C7/413—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
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/3924—Heterocyclic
- G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
- G03C7/39252—Heterocyclic the nucleus containing only nitrogen as hetero atoms two nitrogen atoms
Definitions
- This invention relates to photographic silver halide processing solutions and particularly to colour developing solutions.
- US Patent 4 155 763 describes colour developing solutions comprising an aromatic amine colour developing agent and a 1-aryl-pyrazolidone having two substituents at the 4-position of the pyrazolidon .
- the advantages are said to include faster image dye formation and a more stable colour developing solution.
- a useful group of Type (1) ETA's of formula (I) are those in which at least one of R 1 and/or R 2 is an alkoxy group of 1-4 carbon atoms, eg -OCH3, 3 is hydrogen or an alkyl group of 1-4 carbon atoms, eg - CH3 and R ⁇ is hydrogen or a hydroxyalkyl group of 1-4 carbon atoms, eg -CH2OH.
- the preferred black-and-white developers are: 1- (4-methoxyphenyl)-3-pyrazolidone, l-(3,4-dimethoxy- phenyl)-3-pyrazolidone, and l-phenyl-4-n-pentyl- pyrazolidone.
- the black-and-white developing agent may be present in the developer solution at a concentration up to 5 g/1 preferably in the range 0.05 to 0.5 g/1.
- concentration up to 5 g/1 preferably in the range 0.05 to 0.5 g/1.
- incorporated in the photographic material it may be present in one or more layers thereof. Instead of incorporating them per se in the photographic material they may be, as indicated above, in the form of a
- the present invention is particularly applicable to the processing of colour negative film but is also applicable to other processes, eg colour paper.
- the material to be processed comprises a support bearing at least one silver halide emulsion layer having a colour coupler associated therewith.
- the term "associated therewith” here takes its normal meaning in art.
- the coupler may be incorporated in the emulsion layer or in a layer adjacent thereto.
- the preferred colour materials comprise three dye image forming units each containing one or more emulsion layers having couplers associated therewith and each sensitised to a different region of the spectrum.
- a typical colour material would contain such units sensitised to blue, green and red light and capable of forming yellow, magenta and cyan image dyes respectively.
- a single layer coating of a silver bromoiodide emulsion comprising tabular grains having a mean grain area of 1.05 m ⁇ 2 containing a colour coupler (A) of the formula:
- OC 12 H 25 dissolved in di-tert-butylphthalate (coupler to solvent ratio of 1:0.5) was coated at 1.0 g/m 2 (as silver) and 0.6 g/m 2 of coupler.
- Table 1 below gives process details of concentration of l-(4-methoxyphenyl)-3-pyrazolidone and development time at 37.8°C.
- EXAMPLE 3 A single layer coating of a silver bromoiodide emulsion as described in Example 1 was tested by the procedure of Example 1 was followed except that the time of development was kept constant at 2.5 minutes while varying the CD4 and ETA concentrations as set out in Table 2 below.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Procédé de développement d'un matériau en couleurs à base d'halogénure d'argent comportant une image latente, afin d'obtenir des résultats sensitométriques acceptables à variabilité réduite. Ledit procédé consiste à réaliser un développement en couleurs en présence d'un agent de développement réversal en noir et blanc, ou d'une combinaison de ces agents, ce qui réduit la variabilité des résultats sensitométriques due aux modifications des variables du processus. Il s'agit de préférence du 1-(4-méthoxyphényl)-3-pyrazolidone, du 1-(3,4-diméthoxy-phényl)-3-pyrazolidone, ou du 1-phényl-4-n-pentyl-pyrazolidone.Method for developing a color material based on silver halide comprising a latent image, in order to obtain acceptable sensitometric results with reduced variability. Said method consists in carrying out a development in color in the presence of a reversing development agent in black and white, or a combination of these agents, which reduces the variability of the sensitometric results due to the modifications of the variables of the process. It is preferably 1- (4-methoxyphenyl) -3-pyrazolidone, 1- (3,4-dimethoxy-phenyl) -3-pyrazolidone, or 1-phenyl-4-n-pentyl-pyrazolidone.
Description
METHOD OF PHOTOGRAPHIC SILVER HALIDE PROCESSING, SILVER HALIDE MATERIALS AND SOLUTIONS THEREFOR
This invention relates to photographic silver halide processing solutions and particularly to colour developing solutions.
It is well understood that the parameters of colour development, such as time, temperature, component content, pH, etc have to be carefully controlled in order to obtain consistent sensitometric results. This usually means that there has to be close control over, for example, the temperature and replenishment of colour developing agent. The cost of such control is clearly significant in a commercial operation.
US Patent 4 155 763 describes colour developing solutions comprising an aromatic amine colour developing agent and a 1-aryl-pyrazolidone having two substituents at the 4-position of the pyrazolidon . The advantages are said to include faster image dye formation and a more stable colour developing solution.
The English language abstract of Japanese application 62/178251 describes a colour developing solution comprising a para-phenylenediamine colour developing agent and an auxiliary developing agent including, inter alia, 1-phenyl-pyrazolidone. Image formation is described as "highly sensitive" and forming "excellent gradation". It is also said to be "free from the influence of agitation.
The above two references indicate that the use of a second developing agent in colour developing solutions provides higher developing activity as it would in black and white developer solutions wherein, for example, the activity of a hydroquinone developing
agent is very much increased by the addition of Metol or 1-phenyl-pyrazolidone.
The present invention provides a method of colour development which is less sensitive to variations, for example, of colour developing agent concentration, bromide ion concentration, pH, time of processing and temperature by virtue of the presence of a black-and- white developing agent of a type not previously disclosed for use in a colour developer solution. According to the present invention there is provided a method of developing an imagewise exposed silver halide colour material to provide acceptable sensitometric results with reduced variability which comprises carrying out colour development in the presence of one or a combination of black-and-white silver halide developing agents which reduces the variability of the sensitometric results caused by changes in process variables.
The preferred black-and-white developing agents (alternatively called ETA's (Electron Transfer Agents) herein) are Metol and the pyrazolidones. While most pyrazolidone developing agents show some improvement in achieving less sensitometric variation, those which are particularly effective have the general formula:
(I)
wherein R1 and R2 are each hydrogen or an alkoxy group having 1-4 carbon atoms, and R3 and R^ are each hydrogen or an alkyl group having 1-10 carbon atoms, with the proviso that either one of R1 or R2 is an alkoxy group or one of R***- or R^ are each an alkyl group of 3-7 carbon atoms.
In the present invention (unlike the prior art) not only are the low activity conditions accelerated by the presently used ETA's but also high activity conditions are decelerated thus leading to less variation in sensitometric results under both high and low activity conditions. The black-and-white developer may be present either in the colour developer solution or in the photographic material being processed. When it is incorporated in the photographic material it is preferably in a form which is inactive until processing takes place. For example it could be inactivated by a blocking group which is hydrolysed off when the material is immersed in the developing solution (which is usually alkaline).
The present invention further provides a photographic colour developing solution which comprises a colour developing agent and a black-and- white silver halide developing agent have the general formula:
(I) wherein R1 and R2 are each hydrogen or an alkoxy group having 1-4 carbon atoms, and R and R^ are each hydrogen or an alkyl group having 1-10 carbon atoms, with the proviso that either one of R1 or R2 is an alkoxy group or one of R- or R^ is an alkyl group of 3-7 carbon atoms. A number of ETA's have been examined for their effectiveness in lowering sensitometric sensitivity to process variables. The reduction of sensitivity to development time is used as an example. Three broad types of behaviour for different ETA's can be observed and these are as follows:
(1) A reduction of sensitometric spread with control Dmin increase caused by time and maintenance of aim contrast. See Fig 10 of the accompanying drawings. (2) A reduction of sensitometric spread with control of Dmin increase caused by time and an increase of contrast. See Fig 11 of the accompanying drawings.
(3) A modest reduction in sensitometric spread but with little Dmin control, a reduction in contrast and still a considerable variability. See Fig 12 of the accompanying drawings. These results are clearly
not acceptable particularly with respect to the increase in Dmin. The use of Type (3) ETA's alone is therefore not part of the present invention.
Type (1) is the preferred behaviour exhibited by the preferred compounds. Type (2) is another useful and beneficial behaviour and could, in certain cases, be preferred over Type (1) if an increase in contrast or corresponding trade-off was desired. The present invention also includes the use of combinations of ETA's. Combinations of Type (2) and (3), for example, can give an overall behaviour similar to Type (1). Combinations of Type (1) and (3) also give good results in that the spread of the sensitometric curves is particularly well controlled. A useful group of Type (1) ETA's of formula (I) are those in which at least one of R1 and/or R2 is an alkoxy group of 1-4 carbon atoms, eg -OCH3, 3 is hydrogen or an alkyl group of 1-4 carbon atoms, eg - CH3 and R^ is hydrogen or a hydroxyalkyl group of 1-4 carbon atoms, eg -CH2OH.
A useful group of Type (2) ETA's of formula (I) are those in which R*1- R2 and R3 are hydrogen and R^ is an alkyl group of 3-7 atoms, eg -C5H11
The preferred black-and-white developers are: 1- (4-methoxyphenyl)-3-pyrazolidone, l-(3,4-dimethoxy- phenyl)-3-pyrazolidone, and l-phenyl-4-n-pentyl- pyrazolidone.
The black-and-white developing agent may be present in the developer solution at a concentration up to 5 g/1 preferably in the range 0.05 to 0.5 g/1. When incorporated in the photographic material it may be present in one or more layers thereof. Instead of incorporating them per se in the photographic material they may be, as indicated above, in the form of a
» compound that releases them either as a function of
the pH of the processing solution or as a function of silver halide development.
It has been found, in particular, that the presence of the black-and-white developing agent improves variability caused by variations in time and temperature of development, pH, bromide ion concentration and colour developing agent (eg CD4) concentration in the colour developer solution. The reduced risk of sensitometric variations further means that replenishment rates can be reduced thus resulting in less overflow and effluent. The sometimes needed bromide ion removal from the developer solution may also be avoidable.
The present invention is particularly applicable to the processing of colour negative film but is also applicable to other processes, eg colour paper. The material to be processed comprises a support bearing at least one silver halide emulsion layer having a colour coupler associated therewith. The term "associated therewith" here takes its normal meaning in art. The coupler may be incorporated in the emulsion layer or in a layer adjacent thereto. The preferred colour materials comprise three dye image forming units each containing one or more emulsion layers having couplers associated therewith and each sensitised to a different region of the spectrum. A typical colour material would contain such units sensitised to blue, green and red light and capable of forming yellow, magenta and cyan image dyes respectively.
Examples of colour photographic materials and methods of processing them are described in Research Disclosure Item 308119, December 1989 published by Kenneth Mason Publications, Emsworth, Hants, United a Kingdom.
The following Examples are included for a better understanding of the invention. EXAMPLE 1
A single layer coating of a silver bromoiodide emulsion comprising tabular grains having a mean grain area of 1.05 mμ2 containing a colour coupler (A) of the formula:
Coupler (A)
OC12H25 dissolved in di-tert-butylphthalate (coupler to solvent ratio of 1:0.5) was coated at 1.0 g/m2 (as silver) and 0.6 g/m2 of coupler.
The following basic colour developing solution was used:
Colour Developer
Diethyltriamine pentaacetic acid penta sodium salt (40% w/w) 6.5 ml Potassium carbonate 37.3 g
Sodium bromide 1.3 g
Potassium iodide 1.2 mg
Hydroxylammonium sulphate r 2.0 g
CD4 (colour developing agent) 4.5
Water to 1.0 litre pH=10.0
Table 1 below gives process details of concentration of l-(4-methoxyphenyl)-3-pyrazolidone and development time at 37.8°C.
The sensitometric results for these twelve processes are shown as sets of three time series in Figures 1, 2 and 3 each for a different level of ETA. In Figure 1 (control), without any ETA, the effect of time is considerable giving increases in Dmin, speed, Dmax and contrast. In Figure 2 with 0.1 g/1 of ETA the sensitometric spread caused by time is very much reduced. In Figure 3 with 0.3 g/1 ETA the curves are even closer together. The optimum level of ETA is probably between 0.1 and 0.3 g/1. The essential difference between this result and that expected is that not only do short process times show acceleration
(as might be expected) but the long process times show a reduction (which is not expected).
This unexpected compression of sensitometric spread from both high and low activity conditions is also shown with other process variables as is shown below in Examples 2 and 3.
Similar results were found with the couplers (B) and (C) having the formulae:
cH-i . —t
coated with the same emulsion and processed in the same solution.
EXAMPLE 2
A set of experiments with sodium bromide levels from 0.45 to 2.15 g/1 and ETA levels of 0, 0.1 and 0.3
g/1 was carried out on the same coatings as mentioned above. The results are shown in Figures 4, 5 and 6. Again with zero level of ETA there is a considerable sensitometric spread caused by changing bromide ion level and as the ETA level is increased this is reduced as shown in Figures 5 and 6. The optimum level of ETA is probably between 0.1 and 0.3 g/1.
EXAMPLE 3 A single layer coating of a silver bromoiodide emulsion as described in Example 1 was tested by the procedure of Example 1 was followed except that the time of development was kept constant at 2.5 minutes while varying the CD4 and ETA concentrations as set out in Table 2 below.
The sensitometric results for these fifteen processes are shown as sets of three CD4 level series in Figures 7,8 and 9. In Figure 7 (control) without any ETA the effect of CD4 level is considerable giving increases in Dmin, speed, Dmax and contrast. In
Figure 8 with 0.1 g/1 of ETA the sensitometric spread is caused by CD4 is very much reduced. In Figure 9 with 0.3 g/1 ETA the curves have separated again but are still better than the control especially in similarity of contrast.
Similar results were found with other couplers (B) and (C) coated with the same emulsion and processed in the same solution.
Claims
1. A method of developing an imagewise exposed silver halide colour material to provide acceptable sensitometric results with reduced variability which comprises carrying out colour development in the presence of one or a combination of black-and-white silver halide developing agents which reduces the variability of the sensitometric results caused by changes in process variables.
2. A method as claimed in claim 1 in which the black-and-white developing agent has the general formula:
(I)
wherein R! and R2 are each hydrogen or an alkoxy group having 1-4 carbon atoms, and R-*-- and R^ are each hydrogen or an alkyl group having 1-10 carbon atoms, with the proviso that either one of R1 or R2 is an alkoxy group or one of R*-** or R^ are each an alkyl group of 3-7 carbon atoms.
3. A method as claimed in claim 2 in which at least one of R1 and/or R2 is an alkyoxy group of 1-4 carbon atoms, R***- is hydrogen or an alkyl group of 1-4 carbon atoms, and R^ is hydrogen or a hydroxyalkyl group of
-
1-4 carbon atoms.
4. A method as claimed in claim 2 in which R1- R2 and R3 are hydrogen and R4 is an alkyl group of 3-7 atoms
5. A method as claimed in claim 2 in which the black-and-white developing agent is l-(4- methoxyphenyl)-3-pyrazolidone, l-(3,4-dimethoxy- phenyl)-3-pyrazolidone, or 1-phenyl-4-n-pentyl- pyrazolidone.
6. A method as claimed in any of claims 1-5 in which the black-and-white developing agent is in the colour developer solution.
7. A method as claimed in claim 6 in which the black-and-white developing agent is present in the developer solution at a concentration of from 0.05 to 0.5 g/1.
8. A method as claimed in any of claims 1-5 in which the black-and-white developing agent is incorporated in the silver halide colour material in an inactive form from which the active form is released during processing.
9. A photographic colour developing solution which comprises a colour developing agent and a black-and- white silver halide developing agent have the general formula:
(I) wherein R! and R2 are each hydrogen or an alkoxy group having 1-4 carbon atoms, and R3 and R4 are each hydrogen or an alkyl group having 1-10 carbon atoms, with the proviso that either one of R1 or R2 is an alkoxy group or one of R3 or R4 is an alkyl group of
3-7 carbon atoms.
10. A colour developer solution as claimed in claim 9 in which at least one of R-*- and/or R2 is an alkyoxy group of 1-4 carbon atoms, R3 is hydrogen or an alkyl group of 1-4 carbon atoms, and R4 is hydrogen or a hydroxyalkyl group of 1-4 carbon atoms.
11. A method as claimed in claim 9 in which R1- R2 and R3 are hydrogen and R4 is an alkyl group of 3-7 atoms 12. A method as claimed in any of claims 9-11 in which the black-and-white developing agent is l-(4- methoxyphenyl)-3-pyrazolidone, l-(3,4-dimethoxy- phenyl)-3-pyrazolidone, or l-phenyl-4-n-pentyl- pyrazolidone.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9027062 | 1990-12-13 | ||
| GB909027062A GB9027062D0 (en) | 1990-12-13 | 1990-12-13 | Method of photographic silver halide processing,silver halide materials and solutions therefor |
| PCT/EP1991/002363 WO1992010789A1 (en) | 1990-12-13 | 1991-12-10 | Method of photographic silver halide processing, silver halide materials and solutions therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0561860A1 true EP0561860A1 (en) | 1993-09-29 |
| EP0561860B1 EP0561860B1 (en) | 1995-11-22 |
Family
ID=10686949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92900247A Expired - Lifetime EP0561860B1 (en) | 1990-12-13 | 1991-12-10 | Method of developing silver halide colour photographic materials and use of pyrazolidones |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0561860B1 (en) |
| JP (1) | JPH06503183A (en) |
| DE (1) | DE69114862T2 (en) |
| GB (1) | GB9027062D0 (en) |
| WO (1) | WO1992010789A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69421838T2 (en) * | 1993-03-22 | 2000-06-15 | Eastman Kodak Co., Rochester | Processing method for original photographic elements containing tabular silver chloride grains limited with (100) grain surface |
| US5443943A (en) * | 1993-03-22 | 1995-08-22 | Eastman Kodak Company | Method of processing originating photographic elements containing tabular silver chloride grains bounded by {100} faces |
| GB9306355D0 (en) * | 1993-03-26 | 1993-05-19 | Kodak Ltd | Method of processing photographic silver halide materials |
| GB9408531D0 (en) * | 1994-04-29 | 1994-06-22 | Kodak Ltd | Photographic silver halide colour materials |
| GB9408530D0 (en) * | 1994-04-29 | 1994-06-22 | Kodak Ltd | Photographic silver halide colour material |
| GB9623709D0 (en) * | 1996-11-14 | 1997-01-08 | Kodak Ltd | Novel auxiliary developing agents,photographic materials incorporating them and the use thereof |
| US6087084A (en) * | 1997-11-14 | 2000-07-11 | Eastman Kodak Company | Auxiliary developing agents, photographic materials incorporating them and the use thereof |
| US5994037A (en) * | 1998-10-21 | 1999-11-30 | Eastman Kodak Company | Method for rapid photographic processing with maintained color balance using diffusible photochemicals |
| US6020112A (en) * | 1998-10-21 | 2000-02-01 | Eastman Kodak Company | Method for rapid photographic processing with maintained color balance |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA731087A (en) * | 1959-09-03 | 1966-03-29 | M. Mader Paul | Color development with compositions containing 3-pyrazolidone developing agents |
| US3902905A (en) * | 1972-11-20 | 1975-09-02 | Eastman Kodak Co | Photographic elements containing image dye-providing layer units |
| JPS5943735B2 (en) * | 1976-09-07 | 1984-10-24 | 富士写真フイルム株式会社 | Color photo processing method |
| US4266002A (en) * | 1978-10-02 | 1981-05-05 | Eastman Kodak Company | Substituted 1-phenyl-3-pyrazolidinone electron transfer agents |
| JPS57144547A (en) * | 1981-03-03 | 1982-09-07 | Fuji Photo Film Co Ltd | Silver halide color photosensitive material and its processing method |
| JPS59121328A (en) * | 1982-12-28 | 1984-07-13 | Fuji Photo Film Co Ltd | Photographic sensitive silver halide material |
| JPS60162253A (en) * | 1984-02-01 | 1985-08-24 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photosensitive material |
| JPS62175752A (en) * | 1986-01-29 | 1987-08-01 | Fuji Photo Film Co Ltd | Method for processing silver halide color photographic sensitive material |
| US4912025A (en) * | 1988-06-21 | 1990-03-27 | Eastman Kodak Company | Photographic recording material for accelerated development |
-
1990
- 1990-12-13 GB GB909027062A patent/GB9027062D0/en active Pending
-
1991
- 1991-12-10 JP JP4500379A patent/JPH06503183A/en active Pending
- 1991-12-10 EP EP92900247A patent/EP0561860B1/en not_active Expired - Lifetime
- 1991-12-10 DE DE69114862T patent/DE69114862T2/en not_active Expired - Fee Related
- 1991-12-10 WO PCT/EP1991/002363 patent/WO1992010789A1/en active IP Right Grant
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9210789A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0561860B1 (en) | 1995-11-22 |
| JPH06503183A (en) | 1994-04-07 |
| GB9027062D0 (en) | 1991-02-06 |
| DE69114862T2 (en) | 1996-09-12 |
| WO1992010789A1 (en) | 1992-06-25 |
| DE69114862D1 (en) | 1996-01-04 |
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