US3300307A - Photographic developer composition - Google Patents

Photographic developer composition Download PDF

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Publication number
US3300307A
US3300307A US252340A US25234063A US3300307A US 3300307 A US3300307 A US 3300307A US 252340 A US252340 A US 252340A US 25234063 A US25234063 A US 25234063A US 3300307 A US3300307 A US 3300307A
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US
United States
Prior art keywords
pyrazolidone
emulsion
silver halide
gelatin
phenyl
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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US252340A
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English (en)
Inventor
Jr Albert C Smith
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US252340A priority Critical patent/US3300307A/en
Priority to BE642561A priority patent/BE642561A/xx
Priority to FR960503A priority patent/FR1379533A/fr
Priority to GB1928/64A priority patent/GB1047642A/en
Priority to DEE26242A priority patent/DE1200680B/de
Application granted granted Critical
Publication of US3300307A publication Critical patent/US3300307A/en
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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
    • G03C5/315—Tanning development
    • 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

  • This invention relates to tanning photographic developer-s and particularly to silver halide emulsions containing tanning developers.
  • photographic silver halide developers are recognized as tanning developers including hydroquinone, catec-hol and the like.
  • 4-phenyl catechol has been incorporated in emulsions as disclosed in Yackel, U.S. Patent 2,592,368 issued April 8, 1952.
  • this developer must be dissolved in a coupler solvent and then used as a dispersion in the photographic emulsion.
  • the presence of the coupler solvent tends to make the final coatings softer than desirable
  • the preparation of the dispersion for addition to the emulsion requires colloid which increases the total amount of colloid in the coated emulsion. This is undesirable Where the coatings should be thin and relatively hard.
  • One object of this invention is to provide a new tannin-g developer. emulsion which contains a tanning developer but which results in a relatively hard wash-off relief image and is free from staining.
  • a further object is to provide a combination of gentisic acid with an auxiliary developing agent which can be used in a tanning developer containing silver Additional objects will be halide photographic emulsion. apparent from the following disclosure.
  • a useful concentration range 'for the gentisic acid is from about to 150 grams, with a preferred range of from about 25 to 75 grams .per mole of silver.
  • a useful concentration for the auxiliary developing agent is from about 1 to 25 grams, with a preferred range of from about 2.5 to 10 grams per mole of silver.
  • auxiliary developing agents are known in the art and may he used with gentisic acid, but the preferred auxiliary developing agent is a substituted 3-pyrazolidone having the following general structure
  • Another object is to provide a photographic Y,
  • R groups each represent various substituents such as hydrogen, alkyl or aryl groups
  • R can be hydrogen or a group such as alkyl preferably containing from 1 to 4 carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not
  • R R R and R can be hydrogen atoms, or groups such as an alkyl group preferably of l to 4 carbon atoms or aryl such as phenyl.
  • Example I An unhardened gelatin fine-grain silver chloride photographic emulsion which contained a coating aid and a pyrazo'lidone developing agent was split into two portions. Hydroquinone was added to Portion A and ⁇ gentisic acid was added to Portion B. Both portions were coated on a paper base. Samples of these coatings werelgiven'a reflex exposure to a line copy and immersed in a 4% sodium carbonate activator for one minute and then washed in F. water. It was :found that the sample containing gentisic acid produced sharper and more uniform images than did the hydroquinone-containing sample. It was noticed the hydroquinone-containing coating was very susceptible to aerial oxidation when wet with the alkaline solution, and it exhibited decreased activity after storage.
  • Example 11 An unhardened gelatin silver chloride emulsion which contained a coating aid and a 3-pyrazolidone developing agent was divided into several portions. Gentisic acid was added to one portion while either gallic acid, pyrogallol or catechol were added to other portions of the emulsion. The emulsion samples were then coated on a suitable support and dried. Samples of each of these coatings were tested as described in Example I above. The gentisic :acid coating produced processed samples of good uniformity which were free of stain; whereas, the samples containing either gallic acid, pyrogallol or catechol, due to their instability and solubility under these conditions, exhibited poor uniformity and/or disad vantageous stain.
  • Example III An unh-ardened gelatino silver halide photographic emulsion (predominantly silver chloride), containing one mole of silver halide, 340 grams of gelatin and 5700 grams of water, was jelled, noodled, and washed for onehalf hour with water then melted at 40 C. and the following additions made:
  • This emulsion was coated on a film support and designated Coating A.
  • the treated emulsion was then coated on a film support and designated Coating B.
  • Coatings A and B When processed in an alkaline activator containing sodium carbonate at a pH above 9, Coatings A and B exhibited the following sensitometric characteristics:
  • Coating B exhibited a higher gamma and D than Coating A.
  • Coating A was softer and more subject to physical damage during handling than Coating B due apparently to the pressure of the oily solvent in Coating A which was necessary to disperse the 4- phenyl catechol.
  • the need for additional gelatin in the 4-pheny1 catechol dispersion also renders it difficult to obtain thin, low gelatin-containing coatings.
  • Coatings containing 4-phenyl catechol tend also to be more allergenic than coatings containing gentisic acid, and due to the need for the oil solvent, are more difficult to coat without running into repellancy, etc.; in addition, the incorporated 4-phenyl catechol tanning developer agent has a tendency to autoharden during storage.
  • Example 1V Coatings A and B of Example 3 above were bathed in the alkaline activator, described above, in the dark for one minute. Then the top half of each coating was exposed, while in the activator, to a photoflood lamp at about 12 inches for 4 minutes. The strips were subsequently washed in F. water.
  • the exposed half of Coating B contained an image as evidenced by an overall silver deposit, Whereas, the exposed half of Coating A did not contain an image and was as clear as the unexposed bottom half. It would appear then, that the gentisic acid dilfuses from the emulsion less readily than does the 4-phenyl catechol and is, therefore, available for development after the initial bathing prior to the exposure.
  • Example V A coating was prepared as follows:
  • the resulting melt contained about 4.3 percent gelatin. It was coated on a cellulose triacet-ate film support to give 690 mg. of gelatin per square foot and 400 mg. of silver halide per square foot. The film was exposed to an image and processed in an alkaline activator containing 3 percent sodium carbonate. The non-image areas were then removed by Washing in warm water. This emulsion gave an excellent negative image.
  • Example Vl When either gentisic acid or 4-methyl-1-phenyl-3- pyrazolidone were used separately as in the emulsion of Example I, there was either no image or a very faint image resulting from such use. Alone they are not highly active developing agents at the pH of the activator. The oxidation products of each developing agent, gentisic acid or 4-rnethyl-1-phenyl-3pyrazolidone, are colorless and remain so even when used in combination. When 4-pheny1 catechol hydroquinone, p-phenylenediamine and pyrogallol or gallic acid are used in this system, the oxidation products are colored and produce stain.
  • Example VII Photographic emulsion as in Example I, containing the combination of gentisic acid and 4-methyl-1-phenyl-3- pyrazolidone were compared with 4-phenyl catechol incorporated in similar emulsions in alkaline activator solutions, i.e., 4 percent aqueous sodium carbonate.
  • the developed fogged strips were washed in water at about 90 F. and the emulsion containing the 4-pheny1 catechol was completely washed away, whereas the gentisic acidpyrazolidone containing emulsion was hardened enough to remain on the film support without any reticulation or edge sloughing.
  • film supports such as paper, cellulose ester, plastic supports such as polyethylene, polyethylene terephthalate, etc. These supports may be oxidized, electron bombarded, etc., to improve adhesion.
  • the silver ha lide emulsion may be of the usual negative type or may be a direct positive emulsion.
  • a pigment may be added to the emulsion in order to increase the density if so desired and the support over which the emulsion is coated may have previously been subbed, coated with various coating composition to improve the hydrophilic character of the support or the like.
  • the relief image may be subjected to various treatments known in the art to improve its receptivity to greasy printing inks or the element itself may be subjected to treatments to improve the relative difference in attraction to greasy printing inks to improve the printability of the element for use as a printing plate.
  • FIG. 1 a support is coated with a gelatino-silver halide emulsion 11 containing a substantially water soluble tanning developing agent. This material is exposed and developed by immersion in an alkaline solution to form images of silver and hardened gelatin as shown at 12 in FIG. 2. The remaining unhardened gelatin and silver halide 13 in FIG. 2 is then washed off by treatment of the support with Warm water to leave images 14 of hardened gelatin on the support 10 as shown in FIG. 3.
  • the hydrophilic colloid is preferably gelatin, but may be any other hydrophilic colloid known in the art which is tanned by gelatin tanning agents or may be a combination of gelatin and a similar hydrophilic colloid which would provide a suitable tanning colloid layer.
  • this tanning developer combination is particularly useful in preparing a lithographic printing plate, since a silver halide emulsion incorporating this developer combination provides a hard relief image and can be coated in a relatively thin layer, it will be appreciated that this tanning developer combination may be used in other photographic applications where a tanning developer is desired to be incorporated in the emulsion.
  • Typical emulsions where such a developer would be used are described in Yackel, US. Pat. No. 2,592,368, issued April 8, 1952, and Yutzy et al., U.S. Pat. No. 2,716,059, issued August 23, 1955, and the like.
  • the emulsion vehicle is substantially unhardened this is defined as a meaning not harder than would be the case with gelatin containing 0.25 ounce of formaldehyde (40 percent solution diluted 1 to 3 with water) per pound, when freshly coated, or 0.1 ounce of the solution per pound for a sample aged three to six months.
  • Emulsion layers appreciably harder are not very satisfactory for use in my process or that of the above copending application.
  • the emulsion layer may be exposed in the usual manner under a line drawing and is developed by immersion in an aqueous solution of an alkali such as sodium or potassium carbonate, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, or an amine.
  • an alkali such as sodium or potassium carbonate
  • an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, or an amine.
  • the addition to the alkaline solution, of other materials is also helpful in obtaining a satisfactory relief image.
  • the addition of sodium hydroxide to a sodium carbonate solution improves the sensitometric characteristics of the material as well as the relief properties.
  • reducing agents such as ascorbic acid, hydrazine hydrochloride, sodium sulfite, in small quantities, sodium bicarbonate and urea, are also advantageous.
  • warm water I means water at a temperature above F. to F. or higher.
  • the light-sensitive emulsions are prepared under normal darkroom or safelight conditions as required.
  • emulsions of this invention are useful in the colloid transfer process as described in US. Patents 2,596,- 756 and 2,725,298. sion results in hardening the exposed area of the image which then adheres to the support. The unexposed and, therefore, unhardened area is transferred to a suitable absorbent surface such as a paper receiving sheet when the emulsion is contacted against the paper receiving sheet.
  • a process for providing a relief image comprising developing an exposed silver halide emulsion comprising a substantially unhardened gelatin vehicle and dispersed in said vehicle silver halide and a tanning developing agent comprising gentisic acid and a 3-pyrazolidone silver halide developing agent by imbibing into the gelatin vehicle an aqueous alkaline solution and removing the undeveloped silver halide containing vehicle.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US252340A 1963-01-18 1963-01-18 Photographic developer composition Expired - Lifetime US3300307A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US252340A US3300307A (en) 1963-01-18 1963-01-18 Photographic developer composition
BE642561A BE642561A (en)) 1963-01-18 1964-01-15
FR960503A FR1379533A (fr) 1963-01-18 1964-01-16 Nouvelle émulsion photographique
GB1928/64A GB1047642A (en) 1963-01-18 1964-01-16 Sensitive photographic material
DEE26242A DE1200680B (de) 1963-01-18 1964-01-17 Photographisches Material zur Herstellung eines Reliefbildes

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4283478A (en) * 1978-05-19 1981-08-11 Fuji Photo Film Co., Ltd. Light-sensitive material for preparing a lithographic printing plate and a process using the same
US4427757A (en) 1982-08-27 1984-01-24 Minnesota Mining And Manufacturing Company Tannable imaging element
EP0104351A1 (en) * 1982-08-27 1984-04-04 Minnesota Mining And Manufacturing Company Gelatin silver halide photographic elements for tanning development
US4737441A (en) * 1985-05-30 1988-04-12 Minnesota Mining And Manufacturing Company Photographic material for tanning development and method for obtaining a relief image

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2716059A (en) * 1952-01-21 1955-08-23 Eastman Kodak Co Photographic transfer process
US2751297A (en) * 1953-08-03 1956-06-19 Eastman Kodak Co Photographic emulsion layer containing a 3-pyrazolidone
US3192046A (en) * 1961-08-17 1965-06-29 Eastman Kodak Co Photographic silver halide emulsions sensitized with thioether and developer combinations

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2716059A (en) * 1952-01-21 1955-08-23 Eastman Kodak Co Photographic transfer process
US2751297A (en) * 1953-08-03 1956-06-19 Eastman Kodak Co Photographic emulsion layer containing a 3-pyrazolidone
US3192046A (en) * 1961-08-17 1965-06-29 Eastman Kodak Co Photographic silver halide emulsions sensitized with thioether and developer combinations

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4283478A (en) * 1978-05-19 1981-08-11 Fuji Photo Film Co., Ltd. Light-sensitive material for preparing a lithographic printing plate and a process using the same
US4427757A (en) 1982-08-27 1984-01-24 Minnesota Mining And Manufacturing Company Tannable imaging element
EP0104351A1 (en) * 1982-08-27 1984-04-04 Minnesota Mining And Manufacturing Company Gelatin silver halide photographic elements for tanning development
US4737441A (en) * 1985-05-30 1988-04-12 Minnesota Mining And Manufacturing Company Photographic material for tanning development and method for obtaining a relief image

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Publication number Publication date
GB1047642A (en) 1966-11-09
BE642561A (en)) 1964-05-04
DE1200680B (de) 1965-09-09

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