US2843481A - Photographic processes - Google Patents

Photographic processes Download PDF

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Publication number
US2843481A
US2843481A US444365A US44436554A US2843481A US 2843481 A US2843481 A US 2843481A US 444365 A US444365 A US 444365A US 44436554 A US44436554 A US 44436554A US 2843481 A US2843481 A US 2843481A
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US
United States
Prior art keywords
silver halide
silver
image
hydroxy
developing
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
US444365A
Inventor
Elkan R Blout
Saul G Cohen
Green Milton
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.)
Polaroid Corp
Original Assignee
Polaroid Corp
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 Polaroid Corp filed Critical Polaroid Corp
Priority to US444365A priority Critical patent/US2843481A/en
Priority to US444074A priority patent/US2868077A/en
Priority to GB17383/55A priority patent/GB782217A/en
Priority to DEI10447A priority patent/DE1031637B/en
Priority to FR1134839D priority patent/FR1134839A/en
Application granted granted Critical
Publication of US2843481A publication Critical patent/US2843481A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B30/00—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images
    • G02B30/20—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes
    • G02B30/22—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the stereoscopic type
    • G02B30/25—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the stereoscopic type using polarisation techniques
    • 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
    • G03C5/3014—Hydrazine; Hydroxylamine; Urea; Derivatives thereof
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/25—Dye-imbibition processes; Materials therefor; Preparing or processing such materials
    • 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
    • G03C9/00—Stereo-photographic or similar processes
    • G03C9/04—Vectographic-image

Definitions

  • This invention relates to photography and, more particularly, to compositions and processes useful in the development of photosensitive silver halide elements.
  • a further object of the present invention is to provide novel chemical compounds capable of developing silver halide emulsions.
  • the invention accordingly comprises the several steps and the relation and order of one or more of such steps with respect to each of the others, and the compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • heterocyclic N-hydroxylamines and their salts are effective to develop exposed silver halide emulsions. These compounds contain at least one nitrogen in the ring, are monocyclic and may also contain oxygen in the ring.
  • the preferred heterocyclic N-hydroxylamines are N-hydroxy morpholine, N- hydroxy piperidine and N-hydroxy pyrrolidine, and their salts.
  • novel photographic developing agents of this invention may be prepared as follows:
  • Example 1 Molecular equivalents of pyrolidine and 6% hydrogen peroxide are allowed to stand together at room temperature for 20-24 hours. The solution is then extracted with ether, the ether extract dried, and the ether distilled off. The residue is vacuum fractionated to yield N-hydroxy pyrrolidine. The product boils at 74-76" C. at a pressure of 25 mm. and is soluble in alcohol, ether and alkali and moderately soluble in Water.
  • Example 2 N-hydroxy morpholine is prepared by allowing morpholine and hydrogen peroxide to react in a manner similar to that set forth in Example 1. The product is soluble in alcohol, ether and alkali, moderately soluble in water, and boils at 76-79 C. at a pressure of 3 mm.
  • Example 3 Nhydroxy piperidine is prepared by allowing piperidine and hydrogen peroxide to react in a manner similar to that described in Example 1.
  • the product is soluble in alkali, alcohol and ether, moderately soluble in water, boils at 75-80 C. at a pressure of 18 mm. and melts at 3236 C.
  • This developer composition fully develops a latent image present in a photosensitive silver halide emulsion, such as Kodak Verichrome, in about 5-8 minutes.
  • the relative proportions of the novel developing agents and the other ingredients of the above developer composition may be varied to suit the requirements of the operator.
  • modify the above developer composition by the substitution of preservatives or alkalies other than those specifically mentioned.
  • the above developer composition may be modified by the inclusion of other common components of developer compositions, such as restrainers, accelerators, etc.
  • novel developing agents herein disclosed are colorless, stain-free, stable and relatively nonvolatile (especially in the salt form) and give black silver deposits on development. They may be employed in the form of the free base or as acid salts thereof, such as the oxalate.
  • the salt form may be employed where the developing agent is to be incorporated in, on or behind the emulsion, or Where one desires to prepare a dry leveloper composition, the solvent being added to the dry composition prior to use.
  • Reference in this specification and in the claims to the developing agents in the form of the free base are therefore intended also to include instances where the developing agent is introduced as a salt.
  • an alkaline solution will contain the free base even though it may have been initially added as a salt.
  • heterocyclic N-hyclroxylamines of this invention are also useful as developing agents in diffusion-transfer reversal processes, both dye and silver, and are especially useful in such photographic processes wherein it is desired to eliminate or minimize the need for washing or stabilizing operations in liquid baths subsequent to the formation of the silver print. Examples of such processes are disclosed in U. S. Patent No. 2,647,056 to Edwin H. Land.
  • the utility of the developers of this invention is by no means limited to diffusiontransfer reversal processes, for they may be satisfactorily employed in conventional multistage and multibath photoglraphic processing procedures either in black-andwhile or color photography.
  • a method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion containing a latent image with an aqueous solution containing an alkaline material and a compound selected from the group consisting of N-hydroxy morpholine, N- hydroxy pyrrolidine and N-hydrox'y piperidine for a sufficient time to develop the latent image to a silver image.
  • a method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion containing a latent image with an aqueous solution containing an alkaline material and N-hydroxy pyrrolidine for a suflicient time to develop the latent image to a silver image.
  • a method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion containing a latent image with an aqueous solution containing an alkaline material and N -hydroXy piperidine for a sufficient time to develop the latent image to a silver image.
  • N- hydroXyl heterocyclic amine is selected from the group consisting of N-hydroxy morpholine, N-hydroxy pyrorolidine and N-hydroxy piperidine.

Description

Unite 1 PHUTOGRAPHIC PROCESSES No Drawing. Application July 19, 1954 Serial No. 444,365
Qiairns. ((11. 9629) This invention relates to photography and, more particularly, to compositions and processes useful in the development of photosensitive silver halide elements.
It is one object of the present invention to provide novel compositions and processes employing such novel compositions for the development of silver halide emulsions.
A further object of the present invention is to provide novel chemical compounds capable of developing silver halide emulsions.
Other objects of this invention will in part be obvious and will in part appear hereinafter.
The invention accordingly comprises the several steps and the relation and order of one or more of such steps with respect to each of the others, and the compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
It has noW been discovered that heterocyclic N-hydroxylamines and their salts are effective to develop exposed silver halide emulsions. These compounds contain at least one nitrogen in the ring, are monocyclic and may also contain oxygen in the ring. The preferred heterocyclic N-hydroxylamines are N-hydroxy morpholine, N- hydroxy piperidine and N-hydroxy pyrrolidine, and their salts.
The novel photographic developing agents of this invention may be prepared as follows:
Example 1 Molecular equivalents of pyrolidine and 6% hydrogen peroxide are allowed to stand together at room temperature for 20-24 hours. The solution is then extracted with ether, the ether extract dried, and the ether distilled off. The residue is vacuum fractionated to yield N-hydroxy pyrrolidine. The product boils at 74-76" C. at a pressure of 25 mm. and is soluble in alcohol, ether and alkali and moderately soluble in Water.
Example 2 N-hydroxy morpholine is prepared by allowing morpholine and hydrogen peroxide to react in a manner similar to that set forth in Example 1. The product is soluble in alcohol, ether and alkali, moderately soluble in water, and boils at 76-79 C. at a pressure of 3 mm.
Example 3 Nhydroxy piperidine is prepared by allowing piperidine and hydrogen peroxide to react in a manner similar to that described in Example 1. The product is soluble in alkali, alcohol and ether, moderately soluble in water, boils at 75-80 C. at a pressure of 18 mm. and melts at 3236 C.
The following is an illustration of a photographic developer composition useful in practicing this invention, and is not intended to limit the invention:
2 aten 2 Example 4 Water 7 cc Sodium sulfite grams 10 N-hydroxy morpholine do 0.6 Sodium hydroxide do 0.2
This developer composition fully develops a latent image present in a photosensitive silver halide emulsion, such as Kodak Verichrome, in about 5-8 minutes.
It will be apparent that the relative proportions of the novel developing agents and the other ingredients of the above developer composition may be varied to suit the requirements of the operator. Thus, it is within the scope of this invention to modify the above developer composition by the substitution of preservatives or alkalies other than those specifically mentioned. It is also contemplated that, where desirable, the above developer composition may be modified by the inclusion of other common components of developer compositions, such as restrainers, accelerators, etc.
The novel developing agents herein disclosed are colorless, stain-free, stable and relatively nonvolatile (especially in the salt form) and give black silver deposits on development. They may be employed in the form of the free base or as acid salts thereof, such as the oxalate. Thus, the salt form may be employed where the developing agent is to be incorporated in, on or behind the emulsion, or Where one desires to prepare a dry leveloper composition, the solvent being added to the dry composition prior to use. Reference in this specification and in the claims to the developing agents in the form of the free base are therefore intended also to include instances where the developing agent is introduced as a salt. Thus, an alkaline solution will contain the free base even though it may have been initially added as a salt.
The heterocyclic N-hyclroxylamines of this invention are also useful as developing agents in diffusion-transfer reversal processes, both dye and silver, and are especially useful in such photographic processes wherein it is desired to eliminate or minimize the need for washing or stabilizing operations in liquid baths subsequent to the formation of the silver print. Examples of such processes are disclosed in U. S. Patent No. 2,647,056 to Edwin H. Land. The utility of the developers of this invention, however, is by no means limited to diffusiontransfer reversal processes, for they may be satisfactorily employed in conventional multistage and multibath photoglraphic processing procedures either in black-andwhile or color photography.
As noted above, the herein disclosed novel developing agents are useful in transfer processes of the type disclosed in the said patent to Edwin H. Land, and in other processes in which the problem of a residual stain cannot be readily met by washing operations. When used for transfer purposes, the novel developer compositions of this invention have incorporated therein as a further ingredient a silver halide solvent, such as sodium thiosulfate. If the composition is to be applied to the emulsion by being spread thereon in a thin layer, it may also include a film-forming thickening agent such, for example, as the high molecular weight polymer, sodium carboxymethyl cellulose.
Since certain changes may be made in the above compositions and processes, without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
What is claimed is: i
1. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion containing a latent negative image with an aqueous solution containing an alkaline material and a. monocyclic, N-hydroxyl heterocyclic amine for a sufiicient time to develop the latent image to a silver image.
2. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion containing a latent image with an aqueous solution containing an alkaline material and a compound selected from the group consisting of N-hydroxy morpholine, N- hydroxy pyrrolidine and N-hydrox'y piperidine for a sufficient time to develop the latent image to a silver image.
3. A mehtod of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion containing a latent image with an aqueous solution containing an alkaline material and N-hydroxy morpholine for a sufficient time to develop the latent image to a silver image.
4. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion containing a latent image with an aqueous solution containing an alkaline material and N-hydroxy pyrrolidine for a suflicient time to develop the latent image to a silver image.
5. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion containing a latent image with an aqueous solution containing an alkaline material and N -hydroXy piperidine for a sufficient time to develop the latent image to a silver image.
6. In a process of forming a silver transfer print by a diifusion-transfer reversal process wherein the latent image is developed by an aqueous composition comprising a silver halide developing agent, an alkali and a silver halide solvent, and unexposed silver halide is transferred to an image-receiving layer to form a positive silver image, the improvement which comprises effecting said development using a monocyclic, N-hydroxyl heterocyclic amine as the developing agent.
7. The process as defined in claim 6 wherein said N- hydroXyl heterocyclic amine is selected from the group consisting of N-hydroxy morpholine, N-hydroxy pyrorolidine and N-hydroxy piperidine.
8. The process as defined in claim 6 wherein said developing agent is N-hydroxy morpholine.
9. The process as defined in claim 6 wherein said developing agent is N-hydroxy pyrrolidine.
10. The process as defined in claim 6 wherein said developing agent is N-hydroxy piperidine.
References Cited in the file of this patent OTHER REFERENCES J. Am. Chem. Soc., vol. 72, May 1950, 311. 2280-2281.

Claims (1)

  1. 6. IN A PROCESS OF FORMING A SILVER TRANSFER PRINT BY A DIFFUSION-TRANSFER REVERSAL PROCESS WHEREIN THE LATENT IMAGE IS DEVELOPED BY AN AQUEOUS COMPOSITION COMPRISING A SILVER HALIDE DEVELOPING AGENT, AN ALKALI AND A SILVER HALIDE SOLVENT, AND UNEXPOSED SILVER HALIDE IS TRANSFERRED TO AN IMAGE-RECEIVING LAYER TO FORM A POSITIVE SILVER IMAGE, THE IMPROVEMENT WHICH COMPRISES EFFECTING SAID DEVELOPMENT USING A MONOCYCLIC, N-HYDROXYL HETEROCYCLIC AMINE AS THE DEVELOPING AGENT.
US444365A 1954-07-19 1954-07-19 Photographic processes Expired - Lifetime US2843481A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US444365A US2843481A (en) 1954-07-19 1954-07-19 Photographic processes
US444074A US2868077A (en) 1954-07-19 1954-07-19 Film stock for dichroic dye images
GB17383/55A GB782217A (en) 1954-07-19 1955-06-16 Improvements relating to film stock for dichroic dye images
DEI10447A DE1031637B (en) 1954-07-19 1955-07-18 Film material for dichroic color images
FR1134839D FR1134839A (en) 1954-07-19 1955-07-18 Improvements to a virgin film for obtaining dichroic dye or dye images

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US444365A US2843481A (en) 1954-07-19 1954-07-19 Photographic processes

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DE (1) DE1031637B (en)
FR (1) FR1134839A (en)
GB (1) GB782217A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3362961A (en) * 1963-06-26 1968-01-09 Polaroid Corp N-substituted hydroxylamines
JPS62212363A (en) * 1986-03-11 1987-09-18 Sumitomo Chem Co Ltd Hydroxamic acid compound and prepration thereof
US5618652A (en) * 1995-03-22 1997-04-08 Fuji Photo Film Co., Ltd. Image formation method by silver salt diffusion transfer
WO2003106390A1 (en) * 2002-06-13 2003-12-24 A H Marks & Company Limited Polymerisation inhibitor

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE581344A (en) * 1959-08-04
US3388994A (en) * 1967-02-20 1968-06-18 Polaroid Corp Photographic image-receiving elements having been treated with ammonia after drying

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1658177A (en) * 1923-06-04 1928-02-07 Sulzberger Nathan Photography
US1937844A (en) * 1931-03-23 1933-12-05 Goodrich Co B F Photographic developer and method of developing
US2030336A (en) * 1932-12-24 1936-02-11 Agfa Ansco Corp Photographic developer
US2550617A (en) * 1946-06-06 1951-04-24 Fr Corp Fine grain photographic developer containing morpholine
US2623880A (en) * 1948-12-10 1952-12-30 Hopff Heinrich N-(beta-n'-phenyl-n'-benzylaminoethyl) pyrrolidine
US2648673A (en) * 1950-10-10 1953-08-11 Monsanto Chemicals Nu-thio pyrrolidines

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE656293C (en) * 1934-12-15 1938-02-02 Friedrich Lierg Dr Ing Blank paper for the suction pressure
US2289715A (en) * 1940-06-07 1942-07-14 Polaroid Corp Composite film for receiving stereoscopic prints
BE465036A (en) * 1940-06-07
US2315373A (en) * 1941-05-28 1943-03-30 Polarold Corp Process for forming light-polarizing images

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1658177A (en) * 1923-06-04 1928-02-07 Sulzberger Nathan Photography
US1937844A (en) * 1931-03-23 1933-12-05 Goodrich Co B F Photographic developer and method of developing
US2030336A (en) * 1932-12-24 1936-02-11 Agfa Ansco Corp Photographic developer
US2550617A (en) * 1946-06-06 1951-04-24 Fr Corp Fine grain photographic developer containing morpholine
US2623880A (en) * 1948-12-10 1952-12-30 Hopff Heinrich N-(beta-n'-phenyl-n'-benzylaminoethyl) pyrrolidine
US2648673A (en) * 1950-10-10 1953-08-11 Monsanto Chemicals Nu-thio pyrrolidines

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3362961A (en) * 1963-06-26 1968-01-09 Polaroid Corp N-substituted hydroxylamines
JPS62212363A (en) * 1986-03-11 1987-09-18 Sumitomo Chem Co Ltd Hydroxamic acid compound and prepration thereof
US5618652A (en) * 1995-03-22 1997-04-08 Fuji Photo Film Co., Ltd. Image formation method by silver salt diffusion transfer
WO2003106390A1 (en) * 2002-06-13 2003-12-24 A H Marks & Company Limited Polymerisation inhibitor
US20060167244A1 (en) * 2002-06-13 2006-07-27 Emyr Philips Polymerisation inhibitor

Also Published As

Publication number Publication date
GB782217A (en) 1957-09-04
FR1134839A (en) 1957-04-18
DE1031637B (en) 1958-06-04

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