US2449980A - Removal of photographically active ingredients from gelatin - Google Patents

Removal of photographically active ingredients from gelatin Download PDF

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Publication number
US2449980A
US2449980A US697156A US69715646A US2449980A US 2449980 A US2449980 A US 2449980A US 697156 A US697156 A US 697156A US 69715646 A US69715646 A US 69715646A US 2449980 A US2449980 A US 2449980A
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United States
Prior art keywords
gelatin
active ingredients
finely divided
photographically active
photographically
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Expired - Lifetime
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US697156A
Inventor
Rudolph E Damschroder
Marie E Kauffman
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Priority to BE475968D priority Critical patent/BE475968A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US697156A priority patent/US2449980A/en
Priority to FR966006D priority patent/FR966006A/en
Application granted granted Critical
Publication of US2449980A publication Critical patent/US2449980A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/047Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins

Definitions

  • This "invention relates to'tli' remo'val'of DhOtO- graphically active ingredients front gelatin" or other proteins by treating the gelatifi' or other proteins with certain metals in finely divided form.
  • Photographic en nilsio'ns' are ordinarily prepared by incorporating a photo-sensitive silver saltin-gelatinin aqueous solution as the protective coatin for the photosensitive Silver Salt.
  • A's gelatin is a material which is obtained-from natural sources, there is oftentimes oonsieerame variation in the pro ertiesor that material when used photographically-.-' For instance, some types of" gelatin have therein 91- considerable proportion-of'photogiaphically active ingredients; Because of this-variation it has-heretofore been diflicu-lt to'prepar phot ogra hio emulsion or uniform properties following a 'setfor'mula'for their preparatiom
  • One object of our invention is to provide a method for treating gelatin or other proteins whereby a considerable proportion of'the photographically active ingredients thereof are re moved or renderedinactiv'e: Another object of our invention is tdprovide" a method for new iii'g
  • the gelatin be in liquid form, ordinarily the operation Will be carried out at a temperature within the range of 30-75 C. Ordinarily, the most convenient procedure is to dissolve the protein in an inert solvent and contact the metal particles therewith. Where the protein is water-soluble as in the case oi gelatin, albumin, etc., the use of an aqueous dissolving liquid is desirable. If desired, however, non-aqueous solvents may be used; for instance, gelatin may be dissolved in formamide and treated with the finely divided metal.
  • Gelatins and other proteins vary among themselves as to the degree of photographic activity which is present therein; Accordingly ⁇ - some proteins will nee'd tb be treated for Monger time and with a greater amount of metal per iiiiit weight of protein than-will other rotease ving lesspho'tog'raphic activity.
  • the gelatins or otherproteihs having a highd gree of photographic activity; the use of inetil inanarnount' which will not render the photographically active ingredients entirely inactive vvfl lat least reduce the photographic activity or the gelatin, if only aparti'al reduction inactivity is desired.
  • Our invention' is' adapted to the treatment of various types of' gelatin; 7 For instance, hydroly'ze'd .gelatin's may be treated in accordance with our invention to inactivate onotog'rapm c'a'lly active materials therein as Well as gclatin's which have not been subjectedto hydrolysisan'd which nave-not been subjecte'd to any degrading treatment.
  • Our invention is also adapt ed to the treatment of proteins generally, if desirable, to inactivate the 'photographically"active materials which are present therein; For instance, casein," zein, albimnen, soy bean protein or the like may be treated With'afinely divided metal in accordance with our'inv'ention, I v
  • the metals which are employed to treat gelatin in accordance with our invention should be in a condition in which a large amount of surface is exposed which is ordinarily in a finely divided condition. If the process is operated by incorporating the finely divided metal into the gelatin solution, it is ordinarily desirable to obtain the best results that the particle size of the metal be at least 150-mesh or smaller although in some cases a larger particle size may be desirable.
  • the materials which are suitable for use in our process are those, the sulfides of which, are insoluble in. water and which will not adversely affect a photographic emulsion.
  • the metals which are not suitable are those the sulfides of which are soluble in water or which hydrolyze rapidly in water solution or which have a derogatory effect upon photographic emulsions.
  • Some of the metals which in finely divided form are adapted for use in our process are platinum, nickel, cobalt, cadmium, and silver.
  • One of the finely divided metals which we have found to be particularly suitable in processes in accordance with our invention is Raney nickel which is a well-recognized catalytic material.
  • Another finely divided material which is useful is Adams catalyst, which is finely divided platinum prepared by reducing platinum oxide, also a wellknown catalytic material.
  • Example 1 --1 g. of Raney nickel were stirred into a 12% aqueous gelatin solution made up using 1 pound of dry gelatin. The stirring was continued for hour at 40 C. The solid materials were then removed from the gelatin by filtering through a Kiefer press. The resulting solution was chilled, dried down, and was found to be useful for photographic emulsions, and the photographically active ingredients of that gelatin had been rendered inactive or removed as indicated by the loss in developed silver density of the emulsion made with the treated gelatin as compared to that of the untreated gelatin.
  • Example 2 The procedure of Example 1 was repeated with each of the following metals in finely divided form: cobalt, platinum, lead and ordinary nickel. The gelatin which was obtained in each case was found to be useful for photographic emulsions and the photographically active ingredients thereof had been inactivated.
  • a method of treating a protein having inherent photographically active ingredients therein to render those photographically active ingredients inactive which comprises treating the protein while in solution with a finely divided metal selected from the group consisting of platinum,
  • nickel, cobalt, lead, cadmium, and silver followed by removing the metal particles and any reaction products thereof from the protein.
  • a method of treating gelatin having inherent photographically active ingredients therein to render those photographically active ingredients inactive which comprises treating the gelatin while in solution with a finely divided metal selected from the group consisting of platinum, nickel, cobalt, lead, cadmium, and silver, followed by removing the metal particles and any reaction products thereof from the protein solution.
  • a method of treating gelatin having inherent photographically active ingredients therein to render those photographically active ingredients inactive which comprises treating an aqueous solution of the gelatin with a finely divided metal selected from the group consisting of platinum, nickel, cobalt, lead, cadmium, and silver, followed by removing the metal particles and any reaction products thereof from the gelatin solution.
  • a method of treating gelatin having inherent photographically active ingredients therein to render those ingredients inactive which comprises treating a solution of gelatin having a pH within the range of 4-9 with a finely divided metal selected from the group consisting of platinum, nickel, cobalt, lead, cadmium, and silver, followed by removing the metal particles and any reaction products thereof from the gelatin.
  • a method of treating gelatin having inherent photographically active ingredients therein to render those ingredients inactive which comprises treating an aqueous solution of the gelatin with finely divided Raney nickel, followed by removing the Raney nickel and any reaction prod ucts thereof from the gelatin by filtering.
  • A. method of treating gelatin having inherent photographically active ingredients therein to render those ingredients inactive which comprises treating an aqueous solution of the gelatin with finely divided platinum, followed by remov ing the platinum and any reaction products thereof from the gelatin solution by filtering.
  • a method of treating gelatin having inher ent photographically active ingredients therein to render those ingredients inactive which comprises dissolving the gelatin in water, treating the gelatin for a time with finely divided Raney nickel, and then separating the Raney nickel and any reaction products thereof from the gelatin.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Preparation (AREA)
  • Peptides Or Proteins (AREA)

Description

Patented Sept. 28, 1948 VA OF PIEIQZI GE H AL XA V INGREDIENTS FRQM GELATIN B'Iitdolph fiain'sch'roder and Marie E. Kahl l" manjRochester; N. Y.,assigi 1tii"s to Eastman nouak Coinfiany;=Roches'ter, N: Y., ambit-pom: tion'ofNeW'Jersey. No Drawing. Amnioationsegteiiiuer i4; 1946; Serial No. 697,156
This "invention relates to'tli' remo'val'of DhOtO- graphically active ingredients front gelatin" or other proteins by treating the gelatifi' or other proteins with certain metals in finely divided form.
Photographic en nilsio'ns' are ordinarily prepared by incorporating a photo-sensitive silver saltin-gelatinin aqueous solution as the protective coatin for the photosensitive Silver Salt. A's gelatin is a material which is obtained-from natural sources, there is oftentimes oonsieerame variation in the pro ertiesor that material when used photographically-.-' For instance, some types of" gelatin have therein 91- considerable proportion-of'photogiaphically active ingredients; Because of this-variation it has-heretofore been diflicu-lt to'prepar phot ogra hio emulsion or uniform properties following a 'setfor'mula'for their preparatiom One object of our invention is to provide a method for treating gelatin or other proteins whereby a considerable proportion of'the photographically active ingredients thereof are re moved or renderedinactiv'e: Another object of our invention is tdprovide" a method for new iii'g'gel-atin or other proteins with metals infinely divided condition: Other objects of our' inventio'nliwill appear herein. 7
We" have found that" the photographically act'rveing'redients of' gelati'n or other proteins are 2 either removed "oirender'ed inactive by treating the gelatin or otherpr'oteinswith active metals whose sulfides are insoluble a'ncl'which will not adversely ali'e'ct' the photographic emulsion which is formed therefrom. Our process in its broadest aspectscomprises-treatin the protein either in aqueous or non-aqueous solution in liquid form with one of the metals under the designation given, in finely divided condition and thereafter subjecting the solution to filtration to remove the metal particles therefrom. As it is desirable that the gelatin be in liquid form, ordinarily the operation Will be carried out at a temperature within the range of 30-75 C. Ordinarily, the most convenient procedure is to dissolve the protein in an inert solvent and contact the metal particles therewith. Where the protein is water-soluble as in the case oi gelatin, albumin, etc., the use of an aqueous dissolving liquid is desirable. If desired, however, non-aqueous solvents may be used; for instance, gelatin may be dissolved in formamide and treated with the finely divided metal.
Gelatins and other proteins vary among themselves as to the degree of photographic activity which is present therein; Accordingly}- some proteins will nee'd tb be treated for Monger time and with a greater amount of metal per iiiiit weight of protein than-will other rotease ving lesspho'tog'raphic activity. However, even with the gelatins or otherproteihs having a highd gree of photographic activity; the use of inetil inanarnount' which will not render the photographically active ingredients entirely inactive vvfl lat least reduce the photographic activity or the gelatin, if only aparti'al reduction inactivity is desired. Unless, however, only partial reductioh inactivity is'desired, it is ordinarily oesirable to use a large excess-ofmetal so that every portion of the gelatin or other prbtein'is contacted'with the metal particles.-
Our invention'is' adapted to the treatment of various types of' gelatin; 7 For instance, hydroly'ze'd .gelatin's may be treated in accordance with our invention to inactivate onotog'rapm c'a'lly active materials therein as Well as gclatin's which have not been subjectedto hydrolysisan'd which nave-not been subjecte'd to any degrading treatment. We have found that the treatment iii-accordance with our invent on works e ual y well ongela'tin made'froin different raw stocks, such'as' green, salted calfskin, acidulated bone, or dried hide stock. Our invention is also adapt ed to the treatment of proteins generally, if desirable, to inactivate the 'photographically"active materials which are present therein; For instance, casein," zein, albimnen, soy bean protein or the like may be treated With'afinely divided metal in accordance with our'inv'ention, I v
we have also round that the process wortsvery weli'withih quite'a'reason'able range of on: or ifistaeee; entities with" pH values "within the range of 4 to 9 have been deactivated in accordance with our process, and there has been but little variation in the results obtained. We have found that there is no necessity for adjusting the pH to any particular value in the carrying out of our process. If the metal which is employed is susceptible to the action of acid, it is preferable to treat therewith only those proteins having a pH of above 6.
The metals which are employed to treat gelatin in accordance with our invention should be in a condition in which a large amount of surface is exposed which is ordinarily in a finely divided condition. If the process is operated by incorporating the finely divided metal into the gelatin solution, it is ordinarily desirable to obtain the best results that the particle size of the metal be at least 150-mesh or smaller although in some cases a larger particle size may be desirable.
The materials which are suitable for use in our process are those, the sulfides of which, are insoluble in. water and which will not adversely affect a photographic emulsion. The metals which are not suitable are those the sulfides of which are soluble in water or which hydrolyze rapidly in water solution or which have a derogatory effect upon photographic emulsions. Some of the metals which in finely divided form are adapted for use in our process are platinum, nickel, cobalt, cadmium, and silver. One of the finely divided metals which we have found to be particularly suitable in processes in accordance with our invention is Raney nickel which is a well-recognized catalytic material. Another finely divided material which is useful is Adams catalyst, which is finely divided platinum prepared by reducing platinum oxide, also a wellknown catalytic material.
The following examples illustrate our invention:
Example 1.--1 g. of Raney nickel were stirred into a 12% aqueous gelatin solution made up using 1 pound of dry gelatin. The stirring was continued for hour at 40 C. The solid materials were then removed from the gelatin by filtering through a Kiefer press. The resulting solution was chilled, dried down, and was found to be useful for photographic emulsions, and the photographically active ingredients of that gelatin had been rendered inactive or removed as indicated by the loss in developed silver density of the emulsion made with the treated gelatin as compared to that of the untreated gelatin.
Example 2.The procedure of Example 1 was repeated with each of the following metals in finely divided form: cobalt, platinum, lead and ordinary nickel. The gelatin which was obtained in each case was found to be useful for photographic emulsions and the photographically active ingredients thereof had been inactivated.
It appears that in the process in accordance with our invention there is a chemical combination which takes place between the metal particles and the photographically active materials, and after the treatment of the protein, the metal particles and any reaction product formed therefrom are removed from the mass.
We claim:
1. A method of treating a protein having inherent photographically active ingredients therein to render those photographically active ingredients inactive which comprises treating the protein while in solution with a finely divided metal selected from the group consisting of platinum,
nickel, cobalt, lead, cadmium, and silver, followed by removing the metal particles and any reaction products thereof from the protein.
2. A method of treating gelatin having inherent photographically active ingredients therein to render those photographically active ingredients inactive which comprises treating the gelatin while in solution with a finely divided metal selected from the group consisting of platinum, nickel, cobalt, lead, cadmium, and silver, followed by removing the metal particles and any reaction products thereof from the protein solution.
3. A method of treating gelatin having inherent photographically active ingredients therein to render those photographically active ingredients inactive which comprises treating an aqueous solution of the gelatin with a finely divided metal selected from the group consisting of platinum, nickel, cobalt, lead, cadmium, and silver, followed by removing the metal particles and any reaction products thereof from the gelatin solution.
4. A method of treating gelatin having inherent photographically active ingredients therein to render those ingredients inactive which comprises treating a solution of gelatin having a pH within the range of 4-9 with a finely divided metal selected from the group consisting of platinum, nickel, cobalt, lead, cadmium, and silver, followed by removing the metal particles and any reaction products thereof from the gelatin.
5. A method of treating gelatin having inherent photographically active ingredients therein to render those ingredients inactive, which comprises treating an aqueous solution of the gelatin with finely divided Raney nickel, followed by removing the Raney nickel and any reaction prod ucts thereof from the gelatin by filtering.
6. A. method of treating gelatin having inherent photographically active ingredients therein to render those ingredients inactive, which comprises treating an aqueous solution of the gelatin with finely divided platinum, followed by remov ing the platinum and any reaction products thereof from the gelatin solution by filtering.
'7. A method of treating gelatin having inher ent photographically active ingredients therein to render those ingredients inactive, which comprises dissolving the gelatin in water, treating the gelatin for a time with finely divided Raney nickel, and then separating the Raney nickel and any reaction products thereof from the gelatin.
RUDOLPH E. DAMSCHRODER. MARIE E. KAUFFMAN.
(No references cited.)
US697156A 1946-09-14 1946-09-14 Removal of photographically active ingredients from gelatin Expired - Lifetime US2449980A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BE475968D BE475968A (en) 1946-09-14
US697156A US2449980A (en) 1946-09-14 1946-09-14 Removal of photographically active ingredients from gelatin
FR966006D FR966006A (en) 1946-09-14 1947-09-11 Process for removing photographically active substances from gelatin

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3143423A (en) * 1962-04-02 1964-08-04 Eastman Kodak Co New photo-resist benzoylazide compositions
US3169868A (en) * 1962-04-16 1965-02-16 Eastman Kodak Co Light sensitive photoresist composition
US3271174A (en) * 1963-04-26 1966-09-06 Gen Aniline & Film Corp Process for preparing photographic gelatin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3143423A (en) * 1962-04-02 1964-08-04 Eastman Kodak Co New photo-resist benzoylazide compositions
US3169868A (en) * 1962-04-16 1965-02-16 Eastman Kodak Co Light sensitive photoresist composition
US3271174A (en) * 1963-04-26 1966-09-06 Gen Aniline & Film Corp Process for preparing photographic gelatin

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FR966006A (en) 1950-09-28
BE475968A (en)

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