US2356477A - Hardeners for photographic processing solutions - Google Patents

Hardeners for photographic processing solutions Download PDF

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Publication number
US2356477A
US2356477A US385146A US38514641A US2356477A US 2356477 A US2356477 A US 2356477A US 385146 A US385146 A US 385146A US 38514641 A US38514641 A US 38514641A US 2356477 A US2356477 A US 2356477A
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United States
Prior art keywords
hardening
photographic
layer
solution
exposed
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
Application number
US385146A
Inventor
Cyril J Staud
Popper Catherine Salo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
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Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US385146A priority Critical patent/US2356477A/en
Application granted granted Critical
Publication of US2356477A publication Critical patent/US2356477A/en
Priority to FR953808D priority patent/FR953808A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C5/268—Processing baths not provided for elsewhere, e.g. pre-treatment, stop, intermediate or rinse baths
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners
    • 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
    • G03C5/305—Additives other than developers

Definitions

  • This invention relates to photographic materials and particularly to hardening photographic gelatin or emulsions by adding certain hardening agents to photographic processing solutions.
  • hardening agents to prevent the softening or swelling of photographic emulsion layers during processing, particularly at high temperatures, is well known. Hardening agents are equally suitable for use in the emulsion andv in the developer. Patent 2,063,351, diketone hardening In Stand and Briggs U. S.
  • dialkyldiketones are incorporation in photographic developing solutions or prebaths used to treat the exposed emulsion layer before development.
  • dialkyldiketone hardener is added to an ordinary photographic developing solution or is made up as a separate solution to treat the exposed emulsion before development.
  • a separate solution of the hardener is preferably made up with a small volume of solvent such as water or methyl alcohol and this solution is then diluted to the desired concentration in the developing solution.
  • Hardening agents of the which we have found suitable for use in this way are the following:
  • dialkyldiketone class used for this purpose have been incorporated Acetyl acetone CH3IC OCH2C b-cn.
  • Our hardening agents and method have been found especially suitable for, although not limited to, use with the process of multi-color developement described in Mannes, Godowsky and Wilder U. S. Patent 2,252,718, granted August 19,1941.
  • a photographic film having three superposed emulsion layers sensitive to different regions of the visible spectrum thereon is exposed and developed in a black and white developer, then selectively exposed to the colors to which the layers are sensitive and developed in a color forming developer after each exposure.
  • the top emulsion layer soften during the black and white development step and later to peel from the other emulsion layers.
  • ahardening'agent such as that described in the present application in the first color developer
  • the softening and peeling of the outer emulsion layer is decreased or overcome.
  • diacetyl and other dialkyldiketones were found to be effective in producing sufficient hardness of the top emulsion layer to prevent peeling. This hardening efiect was-produced without interfering with the developing action.
  • the hardening agents which We employ may be used in amounts ranging from 0.15 to 1.5% by weight of the developing solution, the preferred range being from 0.25 to 0.5%.
  • the hardening agents which we use result in overcoming the softening of the emulsion layer tion has been found in some cases'to improve the resolving power of emulsions after processing.
  • Our hardening method may be used not only with sensitive photographic emusions but may also be used to harden non-sensitive photographic gelatin layers, suchas overcoating and backing layers and gelatin layers coated on various supports such as film, paper or cloth.
  • the method of hardening a photographic gelatin layer ofan exposed photographic element including a silver halide layer which comprises treating said gelatin layer with a taining a dialkyl diketone.
  • the method of hardening an exposed gelatino.-silver halide emulsion layer which comprises developing said layer in a photographic developing solution containing a dialkyl diketone.
  • a hardening photographic developing solution comprising an aqueous solution of a, photographic developer containing a dialkyl diketbne.
  • the step of hardening and preventing peeling of the outermost emulsion layer from the underlying emulsion layers which comprises developing said element in a solution of a developing agent and a CYRIL J L STAUD.. CATHERINE SALO POPPER.

Description

" in emulsion layers.
. Diacetyl acetone HARDENERS FOR PHOTOGRAPHIC PROCESSING SOLUTIONS Cyril J. Stand, Rochester, N. Y., and Catherine Salo Popper, Fort Davis, Eastman Kodak Company, corporation of New Jersey Tex, assignors to Rochester, N. Y., a
No Drawing. Application March 25, 1941, Serial No. 385,146
9.Claims.
This invention relates to photographic materials and particularly to hardening photographic gelatin or emulsions by adding certain hardening agents to photographic processing solutions.
The use of hardening agents to prevent the softening or swelling of photographic emulsion layers during processing, particularly at high temperatures, is well known. Hardening agents are equally suitable for use in the emulsion andv in the developer. Patent 2,063,351, diketone hardening In Stand and Briggs U. S.
agents are described-for use Of the diketone compounds described in this patent, we have found that the aromatic diketones are unsuitable for incorporation in developers or prebaths because of incompatibility with the developer or because of lack of hardening action.
It is, therefore, an object of the present invention to provide hardening agents suitable for incorporation in photographic developers or prebaths. Other objects will appear from the following description of our invention.
These objects are accomplished, according to the present invention, by the incorporation of dialkyldiketones in photographic developing solutions or prebaths used to treat the exposed emulsion layer before development.
According to our invention the dialkyldiketone hardener is added to an ordinary photographic developing solution or is made up as a separate solution to treat the exposed emulsion before development. A separate solution of the hardener is preferably made up with a small volume of solvent such as water or methyl alcohol and this solution is then diluted to the desired concentration in the developing solution.
Hardening agents of the which we have found suitable for use in this way are the following:
I Diacetyl Sym.-dicl1lorodiacety1 Cl (EH24: CIElz-CO $1 CHaCOCHa /CO CHaCOCH;
granted December 8, 1936,-
dialkyldiketone class used for this purpose have been incorporated Acetyl acetone CH3IC OCH2C b-cn. Formyl diacetyl methane CHaC 0 Our hardening agents and method have been found especially suitable for, although not limited to, use with the process of multi-color developement described in Mannes, Godowsky and Wilder U. S. Patent 2,252,718, granted August 19,1941. In the process of that application a photographic film having three superposed emulsion layers sensitive to different regions of the visible spectrum thereon, is exposed and developed in a black and white developer, then selectively exposed to the colors to which the layers are sensitive and developed in a color forming developer after each exposure. In this process there is some tendency for the top emulsion layer to soften during the black and white development step and later to peel from the other emulsion layers. Wehave found that by incorporat ing ahardening'agent such as that described in the present application in the first color developer, the softening and peeling of the outer emulsion layer is decreased or overcome. Under the conditions of development used in this processing, that is 10 to 12 minutes at F., diacetyl and other dialkyldiketones were found to be effective in producing sufficient hardness of the top emulsion layer to prevent peeling. This hardening efiect was-produced without interfering with the developing action.
The hardening agents which We employ may be used in amounts ranging from 0.15 to 1.5% by weight of the developing solution, the preferred range being from 0.25 to 0.5%.
The following example of a hardening developer is illustrative: Solution A p-Aminodiethylaniline hydrochloride ams 2 Sodium sulfite do 6 Sodium carbonate do 50 Potassium bromide do 5 Potassium thiocyanate do 1 Diacetyl' dn 1.5 Water to 950 Solution B o-Hydroxydiphenyl grams 3 Sodium hydroxide do 5 Water to 50 (Solution B is added to Solution A.)
The hardening agents which we use result in overcoming the softening of the emulsion layer tion has been found in some cases'to improve the resolving power of emulsions after processing.
Our hardening method may be used not only with sensitive photographic emusions but may also be used to harden non-sensitive photographic gelatin layers, suchas overcoating and backing layers and gelatin layers coated on various supports such as film, paper or cloth.
I It is to be understood that our invention is susceptible of modifications within the scope of the disclosure and claims and that the examples are to be taken as illustrative only.
We claim:
1. The method of hardening a photographic gelatin layer ofan exposed photographic element including a silver halide layer which comprises treating said gelatin layer with a taining a dialkyl diketone.
2. The method of hardening an exposed gela- ,.tino-silver halide emulsion layer which comprises treating said layer with a solution containing a diacetyl.
3. The method of hardening an exposed gelatino-silver halide emulsion layer which comprises treating said layer with a solution containing diacetyl.
solution condialkyl diketone.
4. The method of hardening an exposed gelatino-silver halide emulsion layer which comprises treating said layer with a solution containing symmetricafdichloro diacetyl.
5. The method of hardening an exposed gela tino-silver halide emulsion layer which comprises treating said layer with a solution containing an acetyl acetone. 6; The method of hardening an exposed gelatino-silver halide emulsion layer which comprises treating said layer with a solution containing diacetyl acetone.
'1. The method of hardening an exposed gelatino.-silver halide emulsion layer which comprises developing said layer in a photographic developing solution containing a dialkyl diketone.
8. A hardening photographic developing solution comprising an aqueous solution of a, photographic developer containing a dialkyl diketbne.
9. In the treatment of an exposed multi-layer photographic element having a plurality of differentially-sensitive gelatino-silver halide emulsionlayers on one side of a support, the step of hardening and preventing peeling of the outermost emulsion layer from the underlying emulsion layers, which comprises developing said element in a solution of a developing agent and a CYRIL J L STAUD.. CATHERINE SALO POPPER.
US385146A 1941-03-25 1941-03-25 Hardeners for photographic processing solutions Expired - Lifetime US2356477A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US385146A US2356477A (en) 1941-03-25 1941-03-25 Hardeners for photographic processing solutions
FR953808D FR953808A (en) 1941-03-25 1947-08-04 Tanning agents for gelatin which can be used in particular in photographic baths

Applications Claiming Priority (1)

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US385146A US2356477A (en) 1941-03-25 1941-03-25 Hardeners for photographic processing solutions

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2440954A (en) * 1945-08-23 1948-05-04 Du Pont Process for eliminating stain from color-yielding elements by treatment with aromatic aldehydes containing an acyl group
US2476544A (en) * 1944-11-17 1949-07-19 Gen Aniline & Film Corp Antistain agents for silver bleach solutions
US2657138A (en) * 1950-01-03 1953-10-27 Leonard A Robbins Photographic film developing composition containing beta, beta'-di-chloroethyl ether
US2725305A (en) * 1952-01-02 1955-11-29 Eastman Kodak Co Hardening gelatin emulsions and gelatin solutions
US2962377A (en) * 1954-10-15 1960-11-29 Polaroid Corp Photographic processes and compositions useful therein
US3294536A (en) * 1963-11-04 1966-12-27 Eastman Kodak Co Photographic prehardener compositions

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2476544A (en) * 1944-11-17 1949-07-19 Gen Aniline & Film Corp Antistain agents for silver bleach solutions
US2440954A (en) * 1945-08-23 1948-05-04 Du Pont Process for eliminating stain from color-yielding elements by treatment with aromatic aldehydes containing an acyl group
US2657138A (en) * 1950-01-03 1953-10-27 Leonard A Robbins Photographic film developing composition containing beta, beta'-di-chloroethyl ether
US2725305A (en) * 1952-01-02 1955-11-29 Eastman Kodak Co Hardening gelatin emulsions and gelatin solutions
US2962377A (en) * 1954-10-15 1960-11-29 Polaroid Corp Photographic processes and compositions useful therein
US3294536A (en) * 1963-11-04 1966-12-27 Eastman Kodak Co Photographic prehardener compositions

Also Published As

Publication number Publication date
FR953808A (en) 1949-12-14

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