WO2004001503A1 - Developer concentrate for black and white development of photographic materials - Google Patents
Developer concentrate for black and white development of photographic materials Download PDFInfo
- Publication number
- WO2004001503A1 WO2004001503A1 PCT/EP2003/006007 EP0306007W WO2004001503A1 WO 2004001503 A1 WO2004001503 A1 WO 2004001503A1 EP 0306007 W EP0306007 W EP 0306007W WO 2004001503 A1 WO2004001503 A1 WO 2004001503A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- developer
- pyrazolidone
- phenyl
- methyl
- hydroxymethyl
- Prior art date
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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
- G03C5/266—Supplying of photographic processing chemicals; Preparation or packaging thereof of solutions or concentrates
-
- 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
- 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
- G03C5/3028—Heterocyclic compounds
- G03C5/3035—Heterocyclic compounds containing a diazole ring
Definitions
- the present invention relates to a new aqueous developer concentrate for the black and white development of silver halide photographic materials.
- a developer can comprise different developing agents. Such developing agents are described in Chimie et Physique photographiques, P. Glafkides Chapter LX, pages 152-170, firm edition.
- a main developing agent is used in combination with an auxiliary developing agent.
- auxiliary developer i.e. the combined activity of the mixture of these two agents is greater than the sum of the activities of each of these agents used separately in the same solution. This phenomena called “super-additivity” is explained by Mason in “Photographic Processing Chemistry", Focal Press, London, 1975.
- Polyphenols for example hydroquinone, and reductones, for example compounds of the ascorbic acid type, are the main developers most used in practice in black and white developing solutions.
- aminophenols like Elon® (memyl-p-aminophenol sulfate), l-phenyl-3-pyrazolidones or Phenidones, such as Phenidone-A (l-phenyl-3 pyrazolidone), Phenidone-B (1- phenyl-4 methyl-3 -pyrazolidone), Dimezone (l-phenyl-4,4'-dimethyl-3- pyrazolidone), Dimezone-S (l-phenyl-4-methyl-4'-hydroxymethyl-3- pyrazolidone).
- Photographic developers can be sold as working strength diluted solutions or also be packaged as powders to be dissolved in water or concentrated liquids to be diluted before use.
- the packaging of a developer depends on the solubility and stability of its various components and the user's preferences. The current trend is to reduce the number of components in kits and the volume of the packaging to reduce costs.
- One solution consists in the use of very concentrated developers, but these must then have great stability during storage.
- Conventional 3 -pyrazolidone type co-developers have the disadvantage of having insufficient solubility in water.
- a two-component developer as a powder has the disadvantage of multiplying the packaging, increasing costs and reducing the ease of use.
- Hydroquinone can also be replaced by hydroquinonesulfonic acid or one of its salts.
- GB-A-2,329,973 describes a ready-to-use developer, containing hydroquinonesulfonic acid as main developer and a co-developer that can be 4- methyl-4-hydroxvmethyl-l-phenyl-3 -pyrazolidone.
- a development accelerator that is a polyglycol with average molecular weight between 200 g/mol and 600 g/mol.
- the present invention proposes an aqueous developer concentrate provided as a single part that remains stable and does not have a precipitation problem during storage, and that enables a working strength developer to be obtained keeping a super-additivity effect similar to existing developers and enabling sensitometric results to be obtained comparable to those obtained with hydroquinone type developers for the same processing time without the need to use a development accelerator.
- the aqueous developer concentrate for black and white development is free of hydroquinone, comprises hydroquinonesulfonic acid or one of its salts as main developer, and is characterized in that a) it comprises as co-developer a mixture comprised of 4-methyl-4- hydroxymethyl-1 -phenyl-3 -pyrazolidone and at least one 3 -pyrazolidone type co-developer of formula (I), b) the concentration of 4-methyl-4-hydroxymethyl- 1 -phenyl-3 -pyrazolidone is lower than the solubility of 4-methyl-4-hydroxymethyl-l -phenyl-3 - pyrazolidone measured at 18°C in a developer with composition similar to said developer concentrate but not comprising a co-developer, and c) the quantity of 3 -pyrazolidone type co-developers of formula (I) is between 2 and 60 mole percent in relation to the total quantity of co- developers, the 3 -pyrazolidone type co-developer of formula (I) being:
- R.1 and R.2 each independently represents hydrogen, a substituted or not substituted alkyl group, or a group having the formula:
- n 0 or 1
- L represents a divalent group selected from among 0 0 o
- (Sol) is a solubilizing group selected from among: CO H, SO 3 H, SO 3 K, NHSO R 10 , SO NH 2 , SO 2 HR 10 , polyhydroxyalkyl,
- RlO is alkyl or aryl
- R * is OH, alkyl or aryl
- R*2 is hydrogen, alkyl or aryl
- R3 to R7 in formula (I) each independently represents hydrogen, an alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a group having the formula:
- X represents a divalent group selected from among
- the present invention also relates to a working strength developing solution, obtainable by dilution of the developer concentrate described above.
- the present invention also relates to a process for a black and white photographic development or for the black and white development step of color reversal films and papers comprising contacting an exposed photographic material with a working strength developing solution, obtainable by dilution of the developer concentrate described above.
- the developer concentrate according to the present invention and its working strength solution can be used to develop black and white materials, like graphic arts materials, x-ray materials, black and white photographic films and papers, microfilms or for the black and white development step of color reversal films and papers.
- Figures 1 and 2 represent the sensitometric curves obtained with control developers and with developers according to the present invention used for the black and white development step of color reversal films.
- the aqueous developer concentrate according to the present invention comprises hydroquinonesulfonic acid or one of its salts as main developer of silver halides.
- hydroquinonesulfonic acid or one of its salts as main developer of silver halides.
- potassium hydroquinone-monosulfonate is used.
- the co-developer comprises a mixture of 4-methyl-4- hydroxymethyl- 1 -phenyl-3 -pyrazolidone and a 3 -pyrazolidone type co-developer of formula (I) as defined above.
- These co-developers of formula (I) have solubilizing groups that are generally not directly attached to the phenyl ring or pyrazolidino ring and are described in Patents US-A-5,780,212 and US-A- 5,942,379.
- Examples of 3 -pyrazolidone type compounds of formula (I) useful in the present invention have the following formulas:
- 3 -pyrazolidone type compounds (1) and (17) are especially preferred.
- Other 3 -pyrazolidone type compounds useful in the present invention have the following formulas:
- the concentration of 4-rnethyl ⁇ 4- hydroxymethyl-1 -phenyl-3 -pyrazolidone is lower than the solubility of 4-methyl-4- hydroxymethyl-1 -phenyl-3 -pyrazolidone measured at 18°C in a developer with composition similar to said developer concentrate but not initially comprising a co-developer.
- This solubility was measured by adding 1 gram of 4-methyl-4- hydroxymethyl-1 -phenyl-3 -pyrazolidone to 100 ml of tested developer concentrate. The sample was kept at 18°C and was stirred daily. After one week, the sample was filtered using a 3 ⁇ m filter. The supernatant was analyzed by chromatography.
- the concentration of main developer of hydroquinonesulfonic acid type is between 50 g/1 and 150 g/1, and preferably between 80 g/1 and 120 g/1 and the weight ratio of main developer to 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone is preferably greater than 10 to ensure complete efficiency of the working strength developer.
- the quantity of 3 -pyrazolidone type co-developers of formula (I) is between 2 and 60 mole percent in relation to the total quantity of co-developers.
- One or more 3 -pyrazolidone type co-developers of formula (I) can be used in combination with 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone.
- the developer concentrate according to the invention can contain numerous conventional additives such as an antioxidant, a sequestering agent, a buffering agent, an antifoggant, a solvent, a surfactant, anti-sludging agents, contrast- promoting agents, halides (such as iodide and bromide salts), a silver metal solvent (such as thiocyanates), and other additives known to those skilled in the art.
- the antioxidant can be sulfite or a compound capable of supplying sulfite ions in aqueous solution.
- the antioxidant can be a sulfite, a bisulfite, or a metabisulfite.
- alkali metal or ammonia salts such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium, potassium or ammonium metabisulfite can be used.
- the buffering agent or a compound capable of controlling the pH can be for example a carbonate, a bicarbonate boric acid or a boric acid salt, or an alkanolamine.
- Sequestering agents especially to trap calcium and magnesium ions, can be polyphosphonic acids and aminopolycarboxylic acids and salts thereof.
- composition of the developer concentrate is capable of numerous variants accessible to those skilled in the art according to the planned application.
- the developer concentrate according to the present invention is diluted with water to obtain a working strength solution, just before its use.
- the developer concentrate according to the invention can be diluted up to 10 times with water. Dilution between 5 and 6 times is preferred.
- the working strength developing solution then preferably comprises between 15 g/1 and 25 g/1 of hydroquinonesulfonic acid or one of its salts as main developer, between 0.5 g/1 and 2 g/1 of 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone and between 0.5 g/1 and 2 g/1 of 3 -pyrazolidone type co-developer of formula (I).
- the developer concentrate according to the present invention comprises a quantity of 4-methyl-4-hydroxvmethyl-l -phenyl-3 -pyrazolidone selected to be lower than the solubility of 4-methyl-4-hydroxymethyl-l -phenyl-3 - pyrazolidone in the developer concentrate and to no longer be in supersaturation condition to no longer have a precipitation problem.
- Example 1 Synthesis of the compound [4-[4,4 , -dimethyl-3-oxo-l-pyrazolidinyl]phenyl]amino methanesulfonyl (Compound (1))
- DMSO was degassed by nitrogen bubbling for about 20 minutes.
- potassium t-butoxide (1.8 g, 16 mmol) at ambient temperature, under nitrogen and with stirring.
- the solution was stirred under nitrogen at ambient temperature for 3.5 hours, then added dropwise to tetrahydrofuran (about 800 ml) with rapid stirring.
- a red/brown precipitate was recovered, which was suction washed with THF using a sintered glass funnel. The solid was quickly transferred to a recrystallising dish while it was still damp with THF. Then the solid was dried in a vacuum dryer on phosphorous pentoxide.
- a Kodak Ektachrome 100 ® film was processed according to the Ektachrome E-6® process.
- This process is described in the manual Z-l 19 "Using KODAK Chemicals, Process E-6", Fifth Edition, published by the Eastman Kodak Company.
- This process comprises different successive steps in different baths.
- the first bath corresponds to the first black and white development, this step being performed at 38°C for 6 minutes.
- the control developer (example 3) and the working strength developing solution according to the invention (example 4), both obtained from developer concentrates whose composition is given in table I below, were used respectively.
- the co-developer used in the developer concentrate according to the invention comprised 66.66-mol % of 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone and 33.33-mol % of compound (1).
- 190 ml of corresponding developer concentrate were used diluted with the required amount of water.
- the pH of working strength solutions was 9.68.
- Figure 1 gives the sensitometric curves obtained using, for the first black and white development, the control developer and the developing solution respectively corresponding to examples 3 and 4 for 6 minutes of development. It can be seen that when the developer solution obtained from the developer concentrate according to the invention was used, sensitometric results comparable with the control developer were obtained, for the same processing time.
- the combination of 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone with the compound (1) as co-developers and potassium hydroquinone- monosulfonate as main developer enabled a working strength developer to be obtained keeping the same super-additivity effect as the known control developer.
- the solubility of 4-methyl-4-hydroxymethyl-l -phenyl-3 - pyrazolidone in the developer concentrate was measured by adding 1 gram of 4- methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone to 100 ml of a developer concentrate with composition similar to example 3 but not initially comprising 4- methyl-4-hydroxymethyl- 1 -phenyl-3 -pyrazolidone.
- the sample was kept at 18°C and was stirred daily. After one week, the sample was filtered using a 3 ⁇ m filter. The supernatant was analyzed by chromatography. For the 4-methyl-4- hydroxymethyl-1 -phenyl-3 -pyrazolidone a solubility of about 5.4 g/1 at 18°C was measured.
- the concentration of 4-methyl-4-hydroxymethyl- 1 -phenyl-3 -pyrazolidone was only 5 g/1, and thus lower than its solubility.
- 4-methyl-4-hydroxymethyl-l-phenyl-3- pyrazolidone in the developer concentrate according to the invention was no longer in supersaturation condition.
- the developer concentrate according to the invention does not have a problem of precipitation of 4-methyl-4- hydroxymethyl- 1 -phenyl-3 -pyrazolidone. Examples 5-6
- a Kodak Ektachrome 100S Professional® film was processed according to the Ektachrome E-6® process, using for the first black and white development working strength developing solutions obtained from the developer concentrates whose composition is given in table II below.
- the co-developer used in the developer concentrate according to the invention comprised 55-mol % of 4-methyl-4-hydroxymethyl-l -phenyl-3 - pyrazolidone and 45-mol % of compound (17).
- 190 ml of corresponding developer concentrate were used diluted with the required amount of water.
- the pH of working strength solutions was 9.83.
- Figure 2 gives the sensitometric curves obtained using, for the first black and white development, the control developer and the developing solution respectively corresponding to examples 5 and 6 for 6 minutes of development. It can be seen that when the developing solution obtained from the developer concentrate according to the invention was used, sensitometric results comparable with the control developer were obtained, for the same processing time.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03732552A EP1516227A1 (en) | 2002-06-24 | 2003-06-07 | Developer concentrate for black and white development of photographic materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR02/07768 | 2002-06-24 | ||
FR0207768A FR2841347B1 (en) | 2002-06-24 | 2002-06-24 | DEVELOPER CONCENTRATE FOR THE BLACK AND WHITE DEVELOPMENT OF PHOTOGRAPHIC PRODUCTS |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004001503A1 true WO2004001503A1 (en) | 2003-12-31 |
Family
ID=29719979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/006007 WO2004001503A1 (en) | 2002-06-24 | 2003-06-07 | Developer concentrate for black and white development of photographic materials |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1516227A1 (en) |
FR (1) | FR2841347B1 (en) |
WO (1) | WO2004001503A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0816916A1 (en) * | 1996-06-24 | 1998-01-07 | Eastman Kodak Company | Photographic developing composition |
US5948604A (en) * | 1998-08-11 | 1999-09-07 | Eastman Kodak Company | Single-use processing kit for processing color reversal photographic elements |
US6083673A (en) * | 1996-01-23 | 2000-07-04 | Eastman Kodak Company | Organic/inorganic developer composition |
-
2002
- 2002-06-24 FR FR0207768A patent/FR2841347B1/en not_active Expired - Fee Related
-
2003
- 2003-06-07 EP EP03732552A patent/EP1516227A1/en not_active Withdrawn
- 2003-06-07 WO PCT/EP2003/006007 patent/WO2004001503A1/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6083673A (en) * | 1996-01-23 | 2000-07-04 | Eastman Kodak Company | Organic/inorganic developer composition |
EP0816916A1 (en) * | 1996-06-24 | 1998-01-07 | Eastman Kodak Company | Photographic developing composition |
US5780212A (en) * | 1996-06-24 | 1998-07-14 | Eastman Kodak Company | Photographic developing composition |
US5948604A (en) * | 1998-08-11 | 1999-09-07 | Eastman Kodak Company | Single-use processing kit for processing color reversal photographic elements |
Also Published As
Publication number | Publication date |
---|---|
FR2841347B1 (en) | 2004-11-05 |
FR2841347A1 (en) | 2003-12-26 |
EP1516227A1 (en) | 2005-03-23 |
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