US3829318A - Photoprocessing stabilizer solutions - Google Patents
Photoprocessing stabilizer solutions Download PDFInfo
- Publication number
- US3829318A US3829318A US00291873A US29187372A US3829318A US 3829318 A US3829318 A US 3829318A US 00291873 A US00291873 A US 00291873A US 29187372 A US29187372 A US 29187372A US 3829318 A US3829318 A US 3829318A
- Authority
- US
- United States
- Prior art keywords
- grams
- stabilizer
- solution
- silver halide
- emulsion
- 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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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
- G03C5/38—Fixing; Developing-fixing; Hardening-fixing
- G03C5/39—Stabilising, i.e. fixing without washing out
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/164—Rapid access processing
Definitions
- a typical composition comprises 150-350 grams ammonium thiocyanate, 0.1-1.0 grams l-phenyl- 1,2-tetrazoline-5-thione, and 25-150 grams monobasic potassium phosphate and water to one liter of solution.
- These compositions are particularly useful for the rapid processing of photographic elements wherein the silver halide emulsion layer contains developing agents therein or contiguous thereto as a separate layer. Prints processed with these compositions have been found to be highly resistant to discoloration, fading and staining on both the emulsion and base sides of the print.
- This invention relates to stabilizer solutions useful for photoprocessing and more particularly to improved aqueous, acidic stabilizer solutions for the rapid processing of photosensitive silver halide emulsions.
- these rapid processing methods are accomplished by contacting the exposed photosensitive emulsion with a typical developer composition, or an alkaline activator solution for developing agents in or contiguous to the emulsion, followed by immersion of the emulsion in a stabilizer solution. After stabilization, the print can be dried without performing the conventionally required fixing and washing steps, thereby saving time.
- Prior art stabilizer solutions have traditionally been acidic, aqueous solutions containing high concentrations of a stabilizing agent.
- Common stabilizing agents are compounds containing a double-bonded sulfur or an SH linkage such as alkali metal thiocyanates.
- One of the most commonly used stabilizing agents is ammonium thiocyanate.
- Various acids suchas acetic, propionic, butyric, mucic, citric and tartaric, etc., have been proposed to obtain the desired pH which is well into the acid range.
- an exposed and developed silver halide emulsion can be stabilized to be highly resistant to discoloration, image fading and/or staining by contacting the emulsion with an acidic, aqueous stabilizer composition, comprising, per liter of solution: (1) -350 grams of a water-soluble stabilizing agent, preferably an alkali metal or ammonium thiocyanate; (2) 0.1-1.0 grams of l-phenyl-1,2-tetrazo1ine-5-thione; and, (3) a buffering agent, such as potassium dihydrogen phosphate, present in sufficient quantities to provide a pH between 2.75 and 5 and to provide substantial buffering I during processing of the emulsion.
- a water-soluble stabilizing agent preferably an alkali metal or ammonium thiocyanate
- a buffering agent such as potassium dihydrogen phosphate
- the rapid photoprocessing of a silver halide emulsion in accordance with this invention includes the steps of exposing the photographic element having a light sensitive silver halide emulsion thereon, developing by contact with the developing solution or an activator solution, and stabilization by cont-act with the above-noted stabilizer composition. After the development step, it is desirable to remove excess developing solution present on the surface of the print by convenient means such as a squeegee. After stabilization, the print can be dried directly.
- the light sensitive silver halide emulsions useful for the formation of photographic elements processed with the stabilizer compositions of this invention include any of the known silver halide developing-out emulsions such as silver chloride, -chlorobromide, -chloroiodide, -chloro bromoiodide, -bromide, or -bromoiodide developing-out emulsions. Any of the known permeable hydrophilic colloids can be used for the silver halide emulsions.
- Typical water permeable hydrophilic colloids include gelatin, albumin, polyvinyl alcohol, agar agar, sodium alginate, hydrolyzed cellulose esters, hydrophilic polyvinyl c0- polymers, etc.
- the photographic elements also contain developing agents for the silver halide emulsion, either dispersed in the emulsion layer itself or in layers contiguous thereto coated on the emulsion layer as a separate layer dispersed in another water-permeable hydrophilic colloid layer, or both.
- Useful developing compositions and activator compositions are also well known. Typical are polyhydroxy benzenes such as the hydroquinone, and substituted hydroquinone.
- Substituted hydroquinones include alkyl-substituted hydroquinones, aryl-substituted hydroquinones and other hydrocarbon-substituted hydroquinones, carboxyl-substituted hydroquinones, acyl-substituted hydroquinones, acyloxy-substitu-ted hydroquinones, alkoxysubstituted hydroquinones, halo-substituted hydroquinones, etc.
- Photographic elements and typical developing agents as mentioned above are described in more detail in the patents referred to above and in the following additional patents, the" teachings of which are incorporated by reference: Kennard et al., U.S. 3,192,046; Porter et al., U.S. 3,246,988; Ryan et al., U.S. 3,262,781; and, Porter et al., U.SL 3,291,609.
- the developing agent is dispersed in the emulsion or in a layer contiguous thereto
- the activator may be an alkaline solution such as a solution of sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide or mixtures thereof.
- the silver halide emulsion is not combined with the developing agent, the silver halide emulsion is developed by immersion in a conventional developer such as those enumerated above and known to the art.
- the stabilizer compositions of this invention contain certain specified amounts of a stabilizing agent, l-phenyl-1,2-tetrazoline- -thione and a buffering agent.
- Suitable stabilizing agents for this invention are those water soluble compounds which, when dissolved in acidic solutions, stop or substantially inhibit further development of the silver image and tie up undeveloped silver ions. Usually, these are compounds which contain doublebonded sulfur or an SH linkage; for example, alkali metal or ammonium thiocyanates, thiosulfates, thioureas, or thioglycolic acids. Alkali metal or ammonium thiocyanates are preferred because of their excellent stabilizing properties.
- the stabilizing agent is used in an amount of between about 150 and 350 grams per liter of stabilizing solution.
- This amount is lower than that used in many of the known stabilizer solutions, particularly when the solution is used in an automatic processor which operates at higher than normal speeds, i.e., one which processes 350 square feet or more of silver halide paper per liter of stabilizer solution at a speed of feet per minute.
- the stabilizer compositions of this invention contain from about 0.1 to 1.0 grams per liter of solution of a l-penyl-1,2-tetrazoline-5-thione having the following formula or a tautomeric equivalent thereof:
- the phenyl group may be substituted, as for example where R in the above structural formula is selected from lower alkyls, lower alkoxy, amino or a halogen. These compounds have been found to be particularly efficacious in the reduction or elimination of staining of the silver halide emulsion or base.
- stabilizer compositions are required to be in the acidic pH range to stop the action of the alkaline developer solutions.
- the compositions of this invention include an acidic buffering agent in suflicient amounts to provide the solution with an original pH of between about 2.75 and 5, and also to provide substantial buffering to the stabilizer solution during processing of the silver halide emulsion.
- Some buifering agents which are suitable and known to the art include acetic acid, phosphoric acid and certain of its salts, certain metabisulfites such as alkali metal or ammonium metabisulfites, and some of the other agent is r'rionobasic potassium phosphate (KH PO which has been found to have superior buffering characteristics even over other phosphoric acid salts.
- phosphate has the additional advantages of: (1) not having the objectionable odor of some buffers, such as acetic acid; and (2) not producing volatile gases which are toxic or cause the containers to bulge or split the plastic container under certain environmental conditions, such as some of the metabisulfites.
- the stabilizer compositions of this invention contain about 280:10 grams of a stabiilzing agent, 0510.2 grams of 1-phenyl-l,2-tetrazoline-S-thione, per liter of solution, and a buffering agent sufficient to lower the pH to an original value below about 3.5 and to provide substantial buffering action during processing of the emulsion;
- a stabiilzing agent 0510.2 grams of 1-phenyl-l,2-tetrazoline-S-thione, per liter of solution
- a buffering agent sufficient to lower the pH to an original value below about 3.5 and to provide substantial buffering action during processing of the emulsion
- Stabilizer solution was applied from a dip tray and subsequently squeegeed off after stabilization.
- the stabilizer solution had the following formula:
- the pH of the stabilizer solution was measured after different amounts of paper had been processed. The results were:
- the stabilizer solution is capable of processing large amounts of silver halide stabilization paper before its pH rises to a level making it inefficient for further processing.
- Grams Ammonium thiocyanate 280 D ib asiic sodium phosphate -l 50 l-phenyl-1,2-tetrazoline6-thione 0.5
- Stabilizer pH Paper processed (it?) EXAMPLE 3 The processing conditions and equipment were the same as in Example 1 except that a different stabilizer solution was used which had the following formula:
- Stabilizer pH Paper processed (ft?) 0 EXAMPLE 4 Stabilizer 01- Example Example Example 1 2 3 Original density 0. 60 0. 54 0. 54 Density loss 0. 09 0. 16 0. 14
- An aqueous photoprocessing stabilizer solution comprising, per liter of solution:
- a watersoluble stabilizing agent selected from an alkali metal or ammonium thiocyanate, thiosulfate, thiourea, thioglycol in acid, or combinations of these;
- a buffering agent consisting essentially of from about 25 to about 150 grams of monobasic potassium phosphate.
- An aqueous photoprocessing stabilizer solution comprising, per liter of solution:
- an aqueous, acidic stabilizer composition containing, per liter of solution, from about 150 to about 350 grams of a watersoluble stabilizing agent selected from an alkali metal or ammonium thiocyanate, thiosulfate, thiourea, thioglycolic acid, or cominations of these, from about 0.1 to about 1.0 grams of 1-phenyl-1,2-tetrazoline-5-thi0ne or a tautomeric equivalent thereof, and a buffering agent consisting essentially of from about 25 to about 150 grams of monobasic potassium phosphate.
- a watersoluble stabilizing agent selected from an alkali metal or ammonium thiocyanate, thiosulfate, thiourea, thioglycolic acid, or cominations of these, from about 0.1 to about 1.0 grams of 1-phenyl-1,2-tetrazoline-5-thi0ne or a tautomeric equivalent thereof, and a buffering agent consisting essentially of from about
- said stabilizer composition comprises about 280: 10 grams of ammonium thiocyanate, 0520.2 grams of l-phenyl-1,2-tetrazoline-S-thione and 501-10 grams of monobasic potassium phosphate.
- a process for developing an exposed photographic medium having a photosensitive silver halide emulsion thereon and having developing agents in the silver halide emulsion or in a layer contiguous thereto, comprising,
Abstract
Description
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00291873A US3829318A (en) | 1972-09-25 | 1972-09-25 | Photoprocessing stabilizer solutions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00291873A US3829318A (en) | 1972-09-25 | 1972-09-25 | Photoprocessing stabilizer solutions |
Publications (1)
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US3829318A true US3829318A (en) | 1974-08-13 |
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US00291873A Expired - Lifetime US3829318A (en) | 1972-09-25 | 1972-09-25 | Photoprocessing stabilizer solutions |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4959468A (en) * | 1987-06-12 | 1990-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Color stabilization method for glycoside products |
CN103265409A (en) * | 2013-05-31 | 2013-08-28 | 滁州市润达溶剂有限公司 | Refining method of nonyl phenol |
-
1972
- 1972-09-25 US US00291873A patent/US3829318A/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4959468A (en) * | 1987-06-12 | 1990-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Color stabilization method for glycoside products |
CN103265409A (en) * | 2013-05-31 | 2013-08-28 | 滁州市润达溶剂有限公司 | Refining method of nonyl phenol |
CN103265409B (en) * | 2013-05-31 | 2016-05-11 | 滁州市润达溶剂有限公司 | A kind of process for purification of nonyl phenol |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ITEK GRAPHIX CORP., 800 SOUTH STREET, 5TH FLOOR, W Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ITEK CORPORATION, A CORP OF DE.;REEL/FRAME:004520/0607 Effective date: 19860205 Owner name: ITEK GRAPHIX CORP., A CORP OF DELAWARE,MASSACHUSET Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ITEK CORPORATION, A CORP OF DE.;REEL/FRAME:004520/0607 Effective date: 19860205 |
|
AS | Assignment |
Owner name: A. B. DICK COMPANY, ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ITEK GRAPHIX CORP.;REEL/FRAME:005181/0192 Effective date: 19890401 |
|
AS | Assignment |
Owner name: A. B. DICK COMPANY, ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ITEK GRAPHIX CORP.;REEL/FRAME:005800/0562 Effective date: 19890401 |