EP0654148B1 - Use of ketogluconates in photography - Google Patents
Use of ketogluconates in photography Download PDFInfo
- Publication number
- EP0654148B1 EP0654148B1 EP93916592A EP93916592A EP0654148B1 EP 0654148 B1 EP0654148 B1 EP 0654148B1 EP 93916592 A EP93916592 A EP 93916592A EP 93916592 A EP93916592 A EP 93916592A EP 0654148 B1 EP0654148 B1 EP 0654148B1
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- EP
- European Patent Office
- Prior art keywords
- methyl
- metal salts
- photographic
- ketogluconate
- pyrazolidone
- 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 - Lifetime
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- 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
Definitions
- the present invention relates to the use of derivatives of ketogluconic acid as photographic agents.
- Silver halide emulsions are coated on various papers and films for use in photographic applications. When these emulsions have been exposed to radiation, the sensitized emulsion produces a latent image in the silver halide grains. The image is latent because the grains are sensitized to reduction by the formation of minute quantities of free silver in the grains from the exposure. These grains are developed by placing the exposed photosensitive material in an aqueous solution containing one or more specific reducing chemicals. There are very few reducing agents which will only develop the latent image and not reduce the unexposed silver halide. The reducing agents conventionally employed include such organic materials as hydroquinone and other materials meeting the criteria of the Kendall-Pelz rule.
- Two of these developing agents may be used in the same formulation to produce a result known in the photographic industry as superadditivity, also known as synergy. It is defined as the mixture of two developing agents showing a greater degree of developer activity than the sum of the actions of each agent separately.
- Figs. 1-6 are graphs showing the effect of various ketogluconates on photographic media.
- the present invention is directed to a process for the development of a photographic image on a photographic medium comprising reducing the photosensitized silver on said medium with an effective amount of (a) a compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid, alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers of ketogluconic acid; and C 1 -C 4 alkyl esters of ketogluconic acid and C 1 -C 4 alkyl esters of stereoisomers of ketogluconic acid; and (b) a co-developer.
- a compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid, alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers of ketogluconic acid and C 1 -C 4 alkyl esters of ketogluconic acid and C 1
- the salt of ketogluconic acid is sodium-2-ketogluconate.
- the ester is the methyl ester.
- the methyl ester is methyl-2-ketogluconate.
- the alkaline earth metal salt is calcium-2,5-diketogluconate.
- the co-developer is selected from the group consisting of 4-methylaminophenol, 1-phenyl-3-pyrazolidone, and para-phenylenediamines.
- the present invention is directed to a photographic composition
- a photographic composition comprising (a) an effective amount of a developing agent selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid; alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers thereof; C 1 -C 4 alkyl esters of said salts of ketogluconic acid and stereoisomers thereof; and (b) a co-developer.
- a developing agent selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid; alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers thereof; C 1 -C 4 alkyl esters of said salts of ketogluconic acid and stereoisomers thereof; and (b) a co-developer.
- the co-developer is selected from the group consisting of 4-methylaminophenol, 1-phenyl-3-pyrazolidone, and para-phenylenediamines.
- the present invention is directed to a process for the development of a photographic image on a photographic medium comprising reducing the photosensitized silver on said medium with an effective amount of methyl-2-ketogluconate.
- the present invention is directed to a photographic composition containing an effective amount of methyl-2-ketogluconate as a developing agent.
- ketogluconic acid uses derivatives of ketogluconic acid. These derivatives are used in the form of salts which are hereinafter referred to as either ketogluconates or in the case of the stereoisomers, as ketogulonates.
- keto-gluconates One class of the present developing agents are the alkali metal salts of keto-gluconates, and stereoisomers thereof.
- the D, L and DL forms of the keto-gluconates may be used.
- Stereoisomers of the ketogluconates include the ketogulonates which may also be used in the D, L or DL forms.
- Preferred alkali metal salts are the sodium and potassium salts.
- the sodium and potassium salts of the keto-D-gluconates, keto-L-gluconates, and the keto-DL-gluconates may be used in the composition and process of the present invention.
- the sodium and potassium salts of the keto-D-gulonates, keto-L-gulonates and keto-DL-gulonates may be used in the process and compositions of the present invention.
- Preferred amine salts are the ammonium salts, the triethanolamine salts, the diethylaminoethyl, cyclohexylamine, and the morpholine salts of the ketogluconates and ketogulonates.
- Preferred alkaline earth metal salts are the calcium salts of ketogluconates and ketogulonates.
- ketogluconic acid also exist in the diketo form.
- salts of ketogluconic acid include the diketo salts and esters include the diketo esters.
- esters of the ketogluconates and ketogulonates are the C 1 -C 4 alkyl esters. Preferred is the methyl ester.
- ketogluconic acid is used with a co-developer.
- co-developers are metol (1-phenyl-3 pyrazolidone), a pyrazolidone derivative, phenidone (4-aminomethylphenol), and para-phenylenediamines.
- 3-pyrazolidone silver halide developing agents may be used.
- Examples of such derivatives include: 1-p-tolyl-3-pyrazolidone, 5-phenyl-3-pyrazolidone, 5-met-3-pyrazolidone, 1-p-chlorophenol-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, m-tolyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-tolyl-5-phenyl-3-pyrazolidone, 1-m-tolyl-3-pyrazolidone, 1-p-methoxyphenyl-3-pyrazolidone, 1-acetamidophenyl-3-pyrazolidone, 1-phenyl-2-acetyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-m-aminophenyl-4-4-propyl-3-pyrazolidone, 1-o-chlorophenol--4.methyl-4-eth
- phenylenediamine compounds are N,N-diethyl-p-phenylene-diamine, N,N-diethyl-o-methyl-p-phenylenediamine, N,N-diethyl-methoxy-p-phenylenediamine, P-phenylenediamine, N-ethyl-n-hydroxyethyl-p-phenylenediamine, and N-ethyl-N-hydroxyethyl-o-methyl-p-phenylenediamine.
- photographic media on which images may be developed include black and white print film, color transparencies, black and white transparencies, and color print film.
- the present invention is also directed to a process for developing a photographic image by using methyl-2-ketogluconate as a developer, and to a photographic composition containing methyl-2-ketogluconate as a developing agent.
- the exposure and developing of the film took place in total darkness.
- the film was exposed in a X-Rite 383 sensitometer which has a built in 21 step wedge template.
- the film was then developed in a test formulation for 4 minutes, stopped for 10 seconds, and fixed (Kodak F-5) for 4 minutes. Again the entire development procedure took place at a constant agitation and a temperature of 20 degree C.
- the film was then washed in running water for 20 minutes, squeeged, and dried, and a D log E curve was prepared.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cosmetics (AREA)
Abstract
Description
- The present invention relates to the use of derivatives of ketogluconic acid as photographic agents.
- Development of a photographic image (both negative and positive) is accomplished by selective reduction of light sensitized silver halide to elemental silver. Chemicals capable of this selective reduction are generally of the "Kendall Structure"
X1-(C=C)n-X2
wherein X1 and X2 are hydroxy, amino or substituted amino group and n is either zero or an integer. - Silver halide emulsions are coated on various papers and films for use in photographic applications. When these emulsions have been exposed to radiation, the sensitized emulsion produces a latent image in the silver halide grains. The image is latent because the grains are sensitized to reduction by the formation of minute quantities of free silver in the grains from the exposure. These grains are developed by placing the exposed photosensitive material in an aqueous solution containing one or more specific reducing chemicals. There are very few reducing agents which will only develop the latent image and not reduce the unexposed silver halide. The reducing agents conventionally employed include such organic materials as hydroquinone and other materials meeting the criteria of the Kendall-Pelz rule.
- The structure of developing agents according to the rule are as follows:
a-(A=B)-a'
where - A is carbon,
- B is carbon or nitrogen,
- a and a' are OH, NH2, NHR1, NR1R2.
- Two of these developing agents may be used in the same formulation to produce a result known in the photographic industry as superadditivity, also known as synergy. It is defined as the mixture of two developing agents showing a greater degree of developer activity than the sum of the actions of each agent separately.
- Figs. 1-6 are graphs showing the effect of various ketogluconates on photographic media.
- In one embodiment, the present invention is directed to a process for the development of a photographic image on a photographic medium comprising reducing the photosensitized silver on said medium with an effective amount of (a) a compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid, alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers of ketogluconic acid; and C1-C4 alkyl esters of ketogluconic acid and C1-C4 alkyl esters of stereoisomers of ketogluconic acid; and (b) a co-developer.
- In a preferred process, the salt of ketogluconic acid is sodium-2-ketogluconate.
- In an especially preferred process, the ester is the methyl ester.
- In another preferred process, the methyl ester is methyl-2-ketogluconate.
- In another especially preferred process, the alkaline earth metal salt is calcium-2,5-diketogluconate.
- In a preferred process, the co-developer is selected from the group consisting of 4-methylaminophenol, 1-phenyl-3-pyrazolidone, and para-phenylenediamines.
- In a further embodiment, the present invention is directed to a photographic composition comprising (a) an effective amount of a developing agent selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid; alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers thereof; C1-C4 alkyl esters of said salts of ketogluconic acid and stereoisomers thereof; and (b) a co-developer.
- In a preferred composition the co-developer is selected from the group consisting of 4-methylaminophenol, 1-phenyl-3-pyrazolidone, and para-phenylenediamines.
- In another embodiment, the present invention is directed to a process for the development of a photographic image on a photographic medium comprising reducing the photosensitized silver on said medium with an effective amount of methyl-2-ketogluconate.
- In another embodiment, the present invention is directed to a photographic composition containing an effective amount of methyl-2-ketogluconate as a developing agent.
- The present invention uses derivatives of ketogluconic acid. These derivatives are used in the form of salts which are hereinafter referred to as either ketogluconates or in the case of the stereoisomers, as ketogulonates.
- One class of the present developing agents are the alkali metal salts of keto-gluconates, and stereoisomers thereof. The D, L and DL forms of the keto-gluconates may be used. Stereoisomers of the ketogluconates include the ketogulonates which may also be used in the D, L or DL forms.
- Preferred alkali metal salts are the sodium and potassium salts. The sodium and potassium salts of the keto-D-gluconates, keto-L-gluconates, and the keto-DL-gluconates may be used in the composition and process of the present invention. Similarly, the sodium and potassium salts of the keto-D-gulonates, keto-L-gulonates and keto-DL-gulonates may be used in the process and compositions of the present invention.
- Preferred amine salts are the ammonium salts, the triethanolamine salts, the diethylaminoethyl, cyclohexylamine, and the morpholine salts of the ketogluconates and ketogulonates.
- Preferred alkaline earth metal salts are the calcium salts of ketogluconates and ketogulonates.
- As is well known to these skilled in the art to which this invention applies, the derivatives of ketogluconic acid also exist in the diketo form. Thus, as used herein, salts of ketogluconic acid include the diketo salts and esters include the diketo esters.
- Preferred esters of the ketogluconates and ketogulonates are the C1-C4 alkyl esters. Preferred is the methyl ester.
- The derivatives of ketogluconic acid are used with a co-developer. Preferred co-developers are metol (1-phenyl-3 pyrazolidone), a pyrazolidone derivative, phenidone (4-aminomethylphenol), and para-phenylenediamines.
- Other 3-pyrazolidone silver halide developing agents may be used. Examples of such derivatives include: 1-p-tolyl-3-pyrazolidone, 5-phenyl-3-pyrazolidone, 5-met-3-pyrazolidone, 1-p-chlorophenol-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, m-tolyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-tolyl-5-phenyl-3-pyrazolidone, 1-m-tolyl-3-pyrazolidone, 1-p-methoxyphenyl-3-pyrazolidone, 1-acetamidophenyl-3-pyrazolidone, 1-phenyl-2-acetyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-m-aminophenyl-4-4-propyl-3-pyrazolidone, 1-o-chlorophenol--4.methyl-4-ethyl-3-pyrazolidone, 1-m-acetarnidophenyl-4, 4-diethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4, 4-dimethyl-3-pyrazolidone, 1-p-methoxyphenyl-4, 4-diethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-diphenyl-4,4-dimethyl3-pyrazolidone,1-p-(B-hydroxyethylphenyl)-3-pyrazolidone,1-o-tolyl-3-pyrazolidone,1-o-tolyl-4,4-dimethyl-3-pyrazolidone.
- Examples of phenylenediamine compounds are N,N-diethyl-p-phenylene-diamine, N,N-diethyl-o-methyl-p-phenylenediamine, N,N-diethyl-methoxy-p-phenylenediamine, P-phenylenediamine, N-ethyl-n-hydroxyethyl-p-phenylenediamine, and N-ethyl-N-hydroxyethyl-o-methyl-p-phenylenediamine.
- Examples of photographic media on which images may be developed include black and white print film, color transparencies, black and white transparencies, and color print film.
- It has also been found that the methyl ester of ketogluconic acid, methyl-2-ketogluconate will develop an image without the presence of a co-developer. Thus, the present invention is also directed to a process for developing a photographic image by using methyl-2-ketogluconate as a developer, and to a photographic composition containing methyl-2-ketogluconate as a developing agent.
- Having described the invention in general terms, reference is now made to specific examples. It is to be understood that these examples are not meant to limit the present invention, the scope of which is determined by the appended claims.
- The developing formulations used in these procedures are based on universal developer solutions described in the S.P.S.E. Handbook of Photographic Science and Engineering, Wiley, 1973, page 569. Various derivatives of ketogluconic acid were substituted for those described in the formulations.
- In the test to evaluate the developers on paper, a piece of commercial black and white photographic paper was exposed to a light source from an enlarger at a f-stop of 11 for 30 seconds. A 21 step wedge of various densities was in contact with the paper during exposure. The entire procedure was conducted under safelight conditions. After exposure the paper was developed in the test formulation for 2 minutes. The paper was then placed in an acid stop bath for 10 seconds. Following the stop, the paper was fixed in a Kodak F-5 formulation. The entire development procedure took place in trays placed in a temperature control shaker bath at a constant speed and 20 degree C. The paper was then rinsed in running water for 5 minutes and dried. The densities of the step wedge developed on the paper were then read on a Macbeth TR 924 densitometer. The results of the test were plotted on a D log E curve. The y axis had the values of densities from the relative step exposure on the x axis.
- In order to evaluate our developers on film, the exposure and developing of the film took place in total darkness. The film was exposed in a X-Rite 383 sensitometer which has a built in 21 step wedge template. The film was then developed in a test formulation for 4 minutes, stopped for 10 seconds, and fixed (Kodak F-5) for 4 minutes. Again the entire development procedure took place at a constant agitation and a temperature of 20 degree C. The film was then washed in running water for 20 minutes, squeeged, and dried, and a D log E curve was prepared.
- The following formulations were prepared and used to develop Kodak Polycontrast III RC FM paper.
gram to 500 ml water sodium sulfite 12.5 12.5 12.5 hydroquinone 3.0 methyl-2-ketogluconate 10.0 sodium carbonate 15.0 15.0 15.0 phenidone 0.125 potassium bromide 0.5 0.5 0.5 benzotriazole 0.05 0.5 0.05 potassium hydroxide 3.6 Results of Development Relative Log Exposure Steps Hydroquinone Formulation Phenidone Formulation Densities Methyl-2- ketogluconate Formulation Densities 1 0.03 0.03 0.04 2 0.03 0.03 0.04 3 0.04 0.04 0.05 4 0.12 0.17 0.15 5 0.42 0.49 0.45 6 0.77 0.88 0.80 7 1.15 1.29 1.18 8 1.52 1.65 1.57 9 1.94 1.96 1.99 10 2.05 2.03 2.07 11 2.07 2.04 2.08 - The results of this test indicate that methyl-2-ketogluconate is a developing agent and yields equivalent densities to those of hydroquinone and phenidone. The graph of this example is shown as Fig. 1.
- The following formulations were prepared and used to develop Kodak Tri-X Pan 4164 film.
gram to 500 ml water metol 0.5 0.5 sodium sulfite 12.5 12.5 12.5 methyl-2-ketogluconate 12.0 12.0 sodium carbonate 18.0 18.0 18.0 potassium bromide 0.1875 0.1875 0.1875 Results of Development Relative Log Exposure Steps Metol Formulation Densities Methyl-2-ketogluconate Formulation Densities Metol/methyl-2 ketogluconate Formulation Densities 1 0.06 0.18 2 0.18 0.06 0.20 3 0.23 0.06 0.24 4 0.25 0.06 0.30 5 0.31 0.06 0.40 6 0.33 0.06 0.48 7 0.33 0.06 0.57 8 0.35 0.06 0.65 9 0.40 0.06 0.74 10 0.43 0.06 0.82 11 0.46 0.06 0.94 12 0.50 0.06 1.06 13 0.53 0.06 1.20 14 0.57 0.06 1.34 15 0.61 0.06 1.45 16 0.66 0.06 1.60 17 0.70 0.06 1.72 18 0.74 0.06 1.80 19 0.80 0.06 1.93 20 0.87 0.06 2.06 21 0.93 0.06 2.25 - The results of this test show that methyl-2-ketogluconate has superadditivity with metol, since the sum of the active of the two compounds is greater than either one alone. The graph of the example is shown as Fig. 2.
-
- The table above shows that methyl-2-ketogluconate is a co-developer with phenidone and displays superadditivity. Phenidone is preferred because it is commercially available in large quantities while other known, related developing agents having similar structures and characteristics are not widely available. The graph of the data is shown as Fig. 3.
- The following formulations were prepared and used to develop Kodak Tri-X Pan 4164 film. The formula for N,N-Diethyl-1, 4-phenylenediamine will be abbreviated as DEPDA.
gram to 500 ml water DEPDA 0.241 ml 0.241 ml sodium sulfite 12.5 12.5 12.5 methyl-2-ketogluconate 12.0 12.0 sodium carbonate 18.0 18.0 20.0 potassium bromide 0.1875 0.1875 0.1875 Results of Development Relative Log Exposure Steps DEPDA Formulation Densities Methyl-2-ketogluconate Formulation Densities DEPDA/Methyl-2- ketogluconate Formulation Densities 1 0.12 0.06 0.18 2 0.12 0.06 0.20 3 0.12 0.06 0.22 4 0.14 0.06 0.24 5 0.16 0.06 0.30 6 0.18 0.06 0.34 7 0.19 0.06 0.40 8 0.21 0.06 0.45 9 0.23 0.06 0.51 10 0.25 0.06 0.57 11 0.27 0.06 0.64 12 0.30 0.06 0.71 13 0.32 0.06 0.79 14 0.36 0.06 0.90 15 0.38 0.06 0.99 16 0.40 0.06 1.09 17 0.42 0.06 1.21 18 0.48 0.06 1.36 19 0.51 0.06 1.51 20 0.50 0.06 1.66 21 0.57 0.06 1.85 - These results demonstrate superadditivity of methyl-2-ketogluconate with another developing agent. The graph is shown as Fig. 4.
- The following formulation was prepared and used to develop Kodak Polycontrast III RC FM paper.
grams to 500 ml with water Relative Log Exposure Steps Densities sodium sulfite 12.5 1 0.15 calcium-2,5- 6.0 2 0.21 diketogluconate 3 0.21 sodium carbonate 15.0 4 0.20 potassium bromide 0.5 5 0.57 benzotriazole 0.05 6 0.90 pH to 11.3 with KOH 7 1.26 8 1.66 9 2.00 10 2.07 11 2.08 - This data indicates that other ketogluconates can have activity as photographic developers. The graph is shown as Fig. 5.
- The following formulation was prepared and used to develop Kodak KODAUTH Ortho film, Type 3.
gram to 500 ml with water Relative Log Exposure Steps Densities sodium sulfite 12.5 1 0.24 methyl-2- 2 0.24 diketogluconate 40.0 3 0.24 sodium 4 0.24 carbonate 18.0 5 0.24 potassium 6 0.24 bromide 0.1875 7 0.24 pH 10.5 with KOH 8 0.25 9 0.25 10 0.25 11 0.25 12 0.25 13 0.25 14 0.26 15 0.26 16 0.26 17 0.27 18 0.31 19 0.39 20 0.63 21 1.54 - This data shows that methyl-2-ketogluconate will produce an image on film without co-developers. The graph is shown as Fig. 6.
Claims (10)
- A process for the development of a photographic image on a photographic medium comprising reducing the photosensitized silver on said medium with an effective amount of (a) a compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, and, amine salts of ketogluconic acid; alkali metal salts, alkaline earth metal salts, and, amine salts of stereoisomers of ketogluconic acid, and C1-C4 alkyl esters of ketogluconic acid, C1-C4 alkyl esters of stereoisomers of ketogluconic adid, and (b) a co-developer for said photographic medium.
- A process according to claim 1 wherein said salt of keto-gluconic acid is sodium 2-ketogluconate.
- A process according to claim 1 wherein said ester is the methyl ester.
- A process according to claim 3 wherein said methyl ester is methyl 2-ketogluconate.
- A process according to claim 1 wherein said alkaline earth metal salt is calcium-2,5-diketogluconate.
- A process according to claim 1 wherein said co-developer is selected from the group consisting of methylaminophenol, 1-phenyl-3-pyrazolidone and para-phenylenediamines.
- A photographic material containing an effective amount of a developing agent selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid; alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers thereof; C1-C4 alkyl esters of ketogluconic acid, and C1-C4 alkyl esters of stereoisomers of ketogluconic acids, and (b) a co-developer in said photographic medium.
- A material according to claim 7 where said co-developer is selected from the group consisting of methylaminophenol, 1-phenyl-3-pyrazolidone and para-phenylenediamines.
- A process for the development of a photographic image on a photographic medium comprising reducing the photosensitized silver on said medium with an effective amount of methyl-2-ketogluconate.
- A photographic material containing an effective amount of methyl-2-ketogluconate as a developing agent.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US92609292A | 1992-08-05 | 1992-08-05 | |
US926092 | 1992-08-05 | ||
PCT/US1993/005802 WO1994003834A1 (en) | 1992-08-05 | 1993-06-22 | Use of ketogluconates in photography |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0654148A1 EP0654148A1 (en) | 1995-05-24 |
EP0654148B1 true EP0654148B1 (en) | 1997-10-15 |
Family
ID=25452743
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93916592A Expired - Lifetime EP0654148B1 (en) | 1992-08-05 | 1993-06-22 | Use of ketogluconates in photography |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0654148B1 (en) |
JP (1) | JP2801084B2 (en) |
AT (1) | ATE159350T1 (en) |
AU (1) | AU672418B2 (en) |
CA (1) | CA2140541A1 (en) |
DE (1) | DE69314652T2 (en) |
DK (1) | DK0654148T3 (en) |
ES (1) | ES2111760T3 (en) |
WO (1) | WO1994003834A1 (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1467007A (en) * | 1974-04-18 | 1977-03-16 | Ciba Geigy Ag | Photographic processing method |
US4551411A (en) * | 1984-12-28 | 1985-11-05 | Eastman Kodak Company | Sequestrants used in diffusion transfer elements with metallizable dyes |
SU1381416A1 (en) * | 1986-03-24 | 1988-03-15 | Ленинградский Институт Киноинженеров | Developer=fixer |
US5147767A (en) * | 1991-04-10 | 1992-09-15 | Knapp Audenried W | Gluconic acid-based developer composition |
-
1993
- 1993-06-22 EP EP93916592A patent/EP0654148B1/en not_active Expired - Lifetime
- 1993-06-22 DE DE69314652T patent/DE69314652T2/en not_active Expired - Fee Related
- 1993-06-22 AT AT93916592T patent/ATE159350T1/en not_active IP Right Cessation
- 1993-06-22 JP JP6505287A patent/JP2801084B2/en not_active Expired - Fee Related
- 1993-06-22 DK DK93916592.4T patent/DK0654148T3/en active
- 1993-06-22 WO PCT/US1993/005802 patent/WO1994003834A1/en active IP Right Grant
- 1993-06-22 ES ES93916592T patent/ES2111760T3/en not_active Expired - Lifetime
- 1993-06-22 CA CA002140541A patent/CA2140541A1/en not_active Abandoned
- 1993-06-22 AU AU46390/93A patent/AU672418B2/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
WO1994003834A1 (en) | 1994-02-17 |
JPH07506200A (en) | 1995-07-06 |
DE69314652T2 (en) | 1998-04-16 |
ES2111760T3 (en) | 1998-03-16 |
DK0654148T3 (en) | 1998-06-02 |
JP2801084B2 (en) | 1998-09-21 |
DE69314652D1 (en) | 1997-11-20 |
CA2140541A1 (en) | 1994-02-17 |
ATE159350T1 (en) | 1997-11-15 |
EP0654148A1 (en) | 1995-05-24 |
AU672418B2 (en) | 1996-10-03 |
AU4639093A (en) | 1994-03-03 |
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