US2425363A - Procedure for fixing nongelating emulsions and improved nongelatin emulsion fixing baths - Google Patents

Procedure for fixing nongelating emulsions and improved nongelatin emulsion fixing baths Download PDF

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Publication number
US2425363A
US2425363A US491914A US49191443A US2425363A US 2425363 A US2425363 A US 2425363A US 491914 A US491914 A US 491914A US 49191443 A US49191443 A US 49191443A US 2425363 A US2425363 A US 2425363A
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fixing
emulsions
nongelatin
improved
procedure
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US491914A
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John I Crabtree
George T Eaton
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to GB16827/43A priority Critical patent/GB565146A/en
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Priority to US491914A priority patent/US2425363A/en
Priority to FR926080D priority patent/FR926080A/en
Application granted granted Critical
Publication of US2425363A publication Critical patent/US2425363A/en
Anticipated expiration legal-status Critical
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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
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing

Definitions

  • This invention relates to improved photographic procedure for the treatment of non-gelatin emulsion photographic elements and in particular to improved procedure for fixing such photographic elements.
  • the invention also pertains to improved fixing compositions for such photographic elements.
  • Non-gelatin materials have been used heretofore as protective colloids or carriers as a substitute for gelatin in photographic silver halide emulsions.
  • cellulose esters and synthetic resins such as cellulose nitrate, acetate, acetate-butyrate; polyvinyl acetals such as polyvinyl acetaldehyde acetal and polyvinyl butyraldehyde acetal; cold water solubl polyvinyl acetaldehyde acetal, polyvinyl alcohol and polyvinyl esters such as hydrolized polyvinyl acetate have been used for this purpose.
  • These substitutes are superior to gelatin in many respects but it has been noted that they frequently are not satisfactorily permeated by fixing solutions so that the removal of silver halide by conventional fixing solutions has in many cases been incomplete or required an inordinately long period of time.
  • This invention has for its object to provide improved procedure for the fixing of photographic elements bearing a non-gelatin emulsion. Another object is to provide improved fixing baths which permit rapid fixing of non-gelatin emulsions, and especiall those which have limited permeability to water or to the usual fixing baths. Other objects are to improve the state of the art.
  • our invention includes immersing a photographic element, which comprises a non-gelatin layer containing a developed silver halide photographic image, in a bath which contains a thiocyanate and thiourea as the essential fixing constituents.
  • thiocyanates which may be used are sodium, potassium and ammonium thiocyanate; organic thiocyanates such as thiocyan catechol may be used, but we prefer to use inorganic thiocyanates.
  • Sodium thiocyanate-thiourea mixtures are preferably used in aqueous solutions containing between about 6 and 50% thiocyanate to between about .03 and thiourea.
  • the thiourea may serve as the major constituent in which case between about 2 and 8% thiourea to between about .1 and .5% thiocyanate is preferably employed.
  • amounts in the upper portion of the ranges given for one agent it is preferable to use amounts in the lower portion of the range for the other fixing agent.
  • Fixing baths containing the above-noted proportions of the essential fixing constituents have been tested and in each case have been found to give a fixing time of three to three and one-half minutes or less.
  • the invention is applicable to non-gelatin emulsions in general and will enable shorter fixing times with all such emulsions, It is of particular value in connection with those non-gelatin emulsions which have limited permeability to water.
  • the process of rapidly fixing a photographic element which includes a non-gelatin layer se- 3 lected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which process comprises immersing said photographic element in a bath which containsas the essential fixing constituents between 2.0% and 8.0% thiourea and between .1% and .5% a water essential fixing constituents a water soluble thiocyanate and thiourea.
  • the process of rapidly fixing a photographic element which includes a non-gelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image and having but limited permeability to water
  • a photographic element which includes a non-gelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image and having but limited permeability to water
  • whichprocess comprises immersing said photographic element in a bath which contains as the essential fixing constituents between 6 and 50% water soluble thiocyanate and between .03 ,and 25% thiourea.
  • the process of rapidly fixing a photographic element which includes a non-gelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image and having but limited permeability to water which process comprises immersing said photographic element in a bath which contains as the essential fixing constituents between 2.0% and 8.0% thiourea and between .1% and .5% water soluble thiocyanate.
  • a fixing composition adapted to rapidly fix a photographic element which includes a nongelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which composition comprises a mixture of a water soluble thiocyanate and thiourea.
  • a fixing composition adapted to rapidly fix a photographic element which includes a nongelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which composition comprises between 6 and 50% water soluble thiocyanate and between .03 and 25% thiourea.
  • a fixing composition adapted to rapidly fix a photographic element which includes a nongelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which composition comprises between 2 and 8% thiourea and between 1 and 5% water soluble thiocyanate.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

Patented Aug. 12, 1947 EMULSIONS AND IMPROVED NONGELATIN EMULSION FIXING BATHS John I. Crabtrec and George T. Eaton, Rochester, N. Y., assigno'rs to Eastman Kodak Company, Rochester, N.-Y.,-a corporation of New Jersey No Drawing. (Application June 23, 1943, Serial No. 491,914
9 Claims.
This invention relates to improved photographic procedure for the treatment of non-gelatin emulsion photographic elements and in particular to improved procedure for fixing such photographic elements. The invention also pertains to improved fixing compositions for such photographic elements. 1
Various non-gelatin materials have been used heretofore as protective colloids or carriers as a substitute for gelatin in photographic silver halide emulsions. Thus, cellulose esters and synthetic resins such as cellulose nitrate, acetate, acetate-butyrate; polyvinyl acetals such as polyvinyl acetaldehyde acetal and polyvinyl butyraldehyde acetal; cold water solubl polyvinyl acetaldehyde acetal, polyvinyl alcohol and polyvinyl esters such as hydrolized polyvinyl acetate have been used for this purpose. These substitutes are superior to gelatin in many respects but it has been noted that they frequently are not satisfactorily permeated by fixing solutions so that the removal of silver halide by conventional fixing solutions has in many cases been incomplete or required an inordinately long period of time.
This invention has for its object to provide improved procedure for the fixing of photographic elements bearing a non-gelatin emulsion. Another object is to provide improved fixing baths which permit rapid fixing of non-gelatin emulsions, and especiall those which have limited permeability to water or to the usual fixing baths. Other objects are to improve the state of the art.
These and other objects are accomplished by our invention which includes immersing a photographic element, which comprises a non-gelatin layer containing a developed silver halide photographic image, in a bath which contains a thiocyanate and thiourea as the essential fixing constituents.
In the following examples and description we have given several of the preferred embodiments of our invention, but it is to be understood that these are set forth for the purpose of illustration and not in limitation thereof.
Examples of thiocyanates which may be used are sodium, potassium and ammonium thiocyanate; organic thiocyanates such as thiocyan catechol may be used, but we prefer to use inorganic thiocyanates.
Sodium thiocyanate-thiourea mixtures are preferably used in aqueous solutions containing between about 6 and 50% thiocyanate to between about .03 and thiourea. On the other hand the thiourea may serve as the major constituent in which case between about 2 and 8% thiourea to between about .1 and .5% thiocyanate is preferably employed. When using amounts in the upper portion of the ranges given for one agent it is preferable to use amounts in the lower portion of the range for the other fixing agent. Fixing baths containing the above-noted proportions of the essential fixing constituents have been tested and in each case have been found to give a fixing time of three to three and one-half minutes or less. The exact proportions and quantities used depend upon the composition of the non-gelatin. carriers which have been produced with sufiicient variation in structure to require fixing baths embodying all of the proportions given above, Proportions somewhat outside the ranges given can be used with satisfactory results if slower fixing times can be tolerated. In general the higher the concentration of both of the essential constituents the shorter will be the fixing time. Proportions in the higher ranges are not ordinarily used except for nongelatin emulsions which are very impermeable. The concentrations indicated give a completely clear film free of silver halide in three to three and one-half minutes. Similar tests with a conventional fixing loath containing 30% hypo required an hour for a similar degree of fixing.
The invention is applicable to non-gelatin emulsions in general and will enable shorter fixing times with all such emulsions, It is of particular value in connection with those non-gelatin emulsions which have limited permeability to water.
What we claim is:
1. The process of rapidly fixing a photographic element which includes a non-gelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which process comprises immersing said photographic element in a bath which contains as the essential fixing constituents a Water soluble thiocyanate and thiourea. V
2. The process of rapidly fixing a photographic element which includes a non-gelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which process comprises immersing said photographic element in a bath which contains as the essential fixing constituents between 6 and 50% a water soluble thiocyanate and between .03 and 25% thiourea.
3. The process of rapidly fixing a photographic element which includes a non-gelatin layer se- 3 lected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which process comprises immersing said photographic element in a bath which containsas the essential fixing constituents between 2.0% and 8.0% thiourea and between .1% and .5% a water essential fixing constituents a water soluble thiocyanate and thiourea.
5. The process of rapidly fixing a photographic element which includes a non-gelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image and having but limited permeability to water Whichprocess comprises immersing said photographic element in a bath which contains as the essential fixing constituents between 6 and 50% water soluble thiocyanate and between .03 ,and 25% thiourea.
6. The process of rapidly fixing a photographic element which includes a non-gelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image and having but limited permeability to water which process comprises immersing said photographic element in a bath which contains as the essential fixing constituents between 2.0% and 8.0% thiourea and between .1% and .5% water soluble thiocyanate.
7. A fixing composition adapted to rapidly fix a photographic element which includes a nongelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which composition comprises a mixture of a water soluble thiocyanate and thiourea.
'8. A fixing composition adapted to rapidly fix a photographic element which includes a nongelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which composition comprises between 6 and 50% water soluble thiocyanate and between .03 and 25% thiourea.
9. A fixing composition adapted to rapidly fix a photographic element which includes a nongelatin layer selected from the group consisting of cellulose esters and synthetic resins of limited permeability to water containing a developed silver image which composition comprises between 2 and 8% thiourea and between 1 and 5% water soluble thiocyanate.
JOHN I. CRABTREE. GEORGE T. EATON.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS OTHER REFERENCES Mees, The Theory of the Photographic Process, The Macmillan Co., New York, 1942, pages 462 and 465 cited
US491914A 1943-06-23 1943-06-23 Procedure for fixing nongelating emulsions and improved nongelatin emulsion fixing baths Expired - Lifetime US2425363A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB16827/43A GB565146A (en) 1943-06-23 1943-04-23 Improvements relating to photographic fixing solutions
US491914A US2425363A (en) 1943-06-23 1943-06-23 Procedure for fixing nongelating emulsions and improved nongelatin emulsion fixing baths
FR926080D FR926080A (en) 1943-06-23 1946-04-26 Method and compositions for fixing photographic materials

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2857272A (en) * 1954-09-28 1958-10-21 Rca Corp Electrostatic printing
US2857271A (en) * 1954-09-28 1958-10-21 Rca Corp Electrostatic printing process for producing photographic transparencies
US3259495A (en) * 1962-04-05 1966-07-05 Itek Corp Photothermographic data processing composition, method and article

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2110491A (en) * 1936-04-16 1938-03-08 Eastman Kodak Co Photographic emulsions
US2113312A (en) * 1935-11-02 1938-04-05 Eastman Kodak Co Fine grain photographic developer
US2124608A (en) * 1934-10-27 1938-07-26 Christensen Jens Herman Photographic developer
US2147441A (en) * 1935-10-31 1939-02-14 Hutchison Fine Grain Photo Dev Photographic developer
US2276322A (en) * 1940-08-01 1942-03-17 Eastman Kodak Co Photographic emulsions
US2322084A (en) * 1940-01-11 1943-06-15 Eastman Kodak Co Simultaneous bleaching and fixing bath

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2124608A (en) * 1934-10-27 1938-07-26 Christensen Jens Herman Photographic developer
US2147441A (en) * 1935-10-31 1939-02-14 Hutchison Fine Grain Photo Dev Photographic developer
US2113312A (en) * 1935-11-02 1938-04-05 Eastman Kodak Co Fine grain photographic developer
US2110491A (en) * 1936-04-16 1938-03-08 Eastman Kodak Co Photographic emulsions
US2322084A (en) * 1940-01-11 1943-06-15 Eastman Kodak Co Simultaneous bleaching and fixing bath
US2276322A (en) * 1940-08-01 1942-03-17 Eastman Kodak Co Photographic emulsions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2857272A (en) * 1954-09-28 1958-10-21 Rca Corp Electrostatic printing
US2857271A (en) * 1954-09-28 1958-10-21 Rca Corp Electrostatic printing process for producing photographic transparencies
US3259495A (en) * 1962-04-05 1966-07-05 Itek Corp Photothermographic data processing composition, method and article

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Publication number Publication date
GB565146A (en) 1944-10-27
FR926080A (en) 1947-09-22

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