US1962307A - Photographically sensitive element - Google Patents

Photographically sensitive element Download PDF

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Publication number
US1962307A
US1962307A US615034A US61503432A US1962307A US 1962307 A US1962307 A US 1962307A US 615034 A US615034 A US 615034A US 61503432 A US61503432 A US 61503432A US 1962307 A US1962307 A US 1962307A
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US
United States
Prior art keywords
sulphide
sensitive element
lead
light
coating
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
US615034A
Inventor
Kenneth C D Hickman
Jr Ludwig A Staib
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
Original Assignee
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 US615034A priority Critical patent/US1962307A/en
Priority to DEK130276D priority patent/DE608171C/en
Priority to GB15954/33A priority patent/GB413853A/en
Priority to FR756426D priority patent/FR756426A/en
Application granted granted Critical
Publication of US1962307A publication Critical patent/US1962307A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/725—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing inorganic compounds
    • 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
    • Y10S430/137—Cobalt complex containing

Definitions

  • This invention relates to a positive photo graphic printing process of a novel type.
  • the metal sulphides which are particularly useful are those of lead, copper, bismuth, nickel, mercury and silver. All of these are of a dark color. or coated over, layers containing these sulphides as indicated.
  • reaction in these cases is photochemical, that is, under the action of light the cobalt salt reacts to oxidize the metal sulphide.
  • a suspension of lead sulphide in gelatin is 40 made as follows:
  • Solution A Lead acetate -LQ. 10 grams Gelatin 20 grams Water 100 cc.
  • the mixture is now coated on a support such as paper, for example, in the usual manner, the coating being in a thinlayer. After the coating is dried there is applied to its surface the following:
  • Solution C Hexammine cobaltic chloride saturated solution (at room temperature) Citric acid 5 grams per liter of above Glycerin 3 grams per liter.
  • the paper When this second coating'is dried, the paper is now ready to print. It-is exposed to a light image, as for example, under a negative to a bright light, until the image is'visible. At the. points where the light has acted the dark colored lead sulphide will be bleached. When the printing" is considered complete, the image may be fixed by a thorough washing. The wash,-
  • a ing removes any remaining ,cobalt compound and the layer thereafter has no light sensitivity.
  • any of the metal sulphides mentioned maybe used interchangeably with lead sulphide.
  • the quantity of sulphide used in an emulsion of the type described may be variable. The limits are set only. by practical considerations.
  • the coating made should have sufllcient covering power to make a suitable print, and the coating must of course not be so thick or contain so/much sulphide that the quantity of cobalt salt present is insufficient to bleach or oxidize the sulphide.
  • the various metal sulphides are precipitated from suitable saltsv of the metals by methods if they have no harmful effect on the coating.
  • a photographic light sensitive element comprising a coating containing a heavy metal sulphide selected from the group consisting of lead sulphide, copper sulphide, bismuth sulphide, nickel sulphide, mercury sulphide and silver sulphide, and containing also a light sensitive oxidizing trivalent cobalt salt.
  • a photographic light sensitive element comprising a coating containing a heavymetal sulphide selected from the group consisting of lead sulphide, copper sulphide, bismuth sulphide,
  • nickel sulphide, mercury sulphide and silver sulphide and containing also a light sensitive oxidizing trivalent cobalt salt selected from the group consisting of hexammine cobaltic chloride, nitroso-pentamine cobaltic chloride and trinitro-triamine cobalt.
  • a photographic light sensitive element comprising a coating containing lead sulphide and a light sensitive oxidizing trivalent cobalt salt.
  • a photographic light sensitive element comprising a coating containing lead sulphide and a trivalent cobalt salt selected from the group consisting of hexammine cobaltic chloride, nitroso-pentamine cobaltic chloride and tri-nitrotriamine cobalt.
  • a photographic light sensitive element comprising a coating containing a heavy metal sulphide selected from the group consisting of lead sulphide, copper sulphide, bismuth sulphide, nickel sulphide, mercury sulphide and silver sul- I phide and containing also a light sensitive oxidizing trivalent cobaltsalt and a hygroscopic material.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Coloring (AREA)

Description

June 12, 1934. D. HICKMAN ET AL 7 ,30
PHOTOGRAPHICALLY SENSITIVE ELEMENT Filed June 2, 1932 pkobsensilive hyer Patented June 12, 1934 PHOTOGRAPHICALLY SENSITIVE ELEMENT Kenneth C. D. Hickman, Rochester, N. Y., and Ludwig A. Staib, Jr., Baltimore, Md., assignors to Eastman Kodak Company, Rochester, N. Y.,
a corporation of New York Application June 2, 1932, Serial No..615,034
Claims.
This invention relates to a positive photo graphic printing process of a novel type.
A positive printing process in which a black material would be bleached as a result of ex-' 5 posure to light has long been desired. We have now found a means of producing such a material of a useful sort.
We have discovered that certain heavy metal sulphides which are brown or black, may be oxidized to a white material, probably the corresponding sulphate, under the action of light, by certainsalts. These salts are trivalent cobalt salts and through a photochemical reaction induced by light they oxidize the metal sulphide. Among the salts which we have found accomplish the oxidation are hexammine cobaltic-chloride [Co (NI-I3) e013], nitrosopentamine cobaltic chloride [C0(NH3)5NO]C12, and trinitro-triamine cobalt [CQ(NH3) 3(NO2) a].
The metal sulphides which are particularly useful are those of lead, copper, bismuth, nickel, mercury and silver. All of these are of a dark color. or coated over, layers containing these sulphides as indicated.
The reaction in these cases is photochemical, that is, under the action of light the cobalt salt reacts to oxidize the metal sulphide. It
' is thus seen that it is possible to produce a darkcolored coating of the metal sulphide containing one of these cobalt salts and by expo- .sure to light to obtain a white design against a black background, the white portions corresponding to the areas of greatest light action. This we have made the basis of a practical printing method.
The following is illustrative of one method of carrying out our invention;
A suspension of lead sulphide in gelatin is 40 made as follows:
Solution A Lead acetate -LQ. 10 grams Gelatin 20 grams Water 100 cc.
After the solution of the gelatine and the lead acetate there is added to this solution the following:
Sodium sulphide 10 grams Gelatin 20 grams Water 100 cc.
After Solution B has been added to Solution A, as indicated, the entire solution is allowed to The cobalt salts are added to,
set. It is then shredded, washed and remelted,- in the manner well-known to photographic emulsion makers.
The mixture is now coated on a support such as paper, for example, in the usual manner, the coating being in a thinlayer. After the coating is dried there is applied to its surface the following:
Solution C Hexammine cobaltic chloride saturated solution (at room temperature) Citric acid 5 grams per liter of above Glycerin 3 grams per liter.
When this second coating'is dried, the paper is now ready to print. It-is exposed to a light image, as for example, under a negative to a bright light, until the image is'visible. At the. points where the light has acted the dark colored lead sulphide will be bleached. When the printing" is considered complete, the image may be fixed by a thorough washing. The wash,-
A ing removes any remaining ,cobalt compound and the layer thereafter has no light sensitivity.
Instead of the procedure outlined above, the emulsion of lead sulphide made as above by mixing Solutions Aand B has added to it the cobalt compound. To accomplish this it is only necessary to add to the mixed emulsion (Solution-A Solution B) an equal volume of Solution 0. The completed emulsion containing the cobalt salt is then coated and is ready for printing as before. i
The single figure of the accompanying drawing shows in section and 'on an exaggerated scale a sensitiveelement embodying our invention.
In following out the process described it is, .of course, necessary to add a s'umcient quantity of cobalt salt to oxidize all ofthe lead sulphide to lead sulphate. Otherwise, it would not be possible to obtain clean whites in the print.
' Any of the metal sulphides mentioned maybe used interchangeably with lead sulphide. The quantity of sulphide used in an emulsion of the type described may be variable. The limits are set only. by practical considerations. The coating made should have sufllcient covering power to make a suitable print, and the coating must of course not be so thick or contain so/much sulphide that the quantity of cobalt salt present is insufficient to bleach or oxidize the sulphide. The various metal sulphides are precipitated from suitable saltsv of the metals by methods if they have no harmful effect on the coating.
We consider as included within our invention all modifications and equivalents coming within the scope of the appended claims.
What we claim is:
1. A photographic light sensitive element comprising a coating containing a heavy metal sulphide selected from the group consisting of lead sulphide, copper sulphide, bismuth sulphide, nickel sulphide, mercury sulphide and silver sulphide, and containing also a light sensitive oxidizing trivalent cobalt salt.
2. A photographic light sensitive element comprising a coating containing a heavymetal sulphide selected from the group consisting of lead sulphide, copper sulphide, bismuth sulphide,
nickel sulphide, mercury sulphide and silver sulphide, and containing also a light sensitive oxidizing trivalent cobalt salt selected from the group consisting of hexammine cobaltic chloride, nitroso-pentamine cobaltic chloride and trinitro-triamine cobalt.
-3. A photographic light sensitive element comprising a coating containing lead sulphide and a light sensitive oxidizing trivalent cobalt salt.
4. A photographic light sensitive element comprising a coating containing lead sulphide and a trivalent cobalt salt selected from the group consisting of hexammine cobaltic chloride, nitroso-pentamine cobaltic chloride and tri-nitrotriamine cobalt.
5. A photographic light sensitive element comprising a coating containing a heavy metal sulphide selected from the group consisting of lead sulphide, copper sulphide, bismuth sulphide, nickel sulphide, mercury sulphide and silver sul- I phide and containing also a light sensitive oxidizing trivalent cobaltsalt and a hygroscopic material.
KENNETH C. D. HICKMAN. LUDWIG A. STAIB, Ja.
US615034A 1932-06-02 1932-06-02 Photographically sensitive element Expired - Lifetime US1962307A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US615034A US1962307A (en) 1932-06-02 1932-06-02 Photographically sensitive element
DEK130276D DE608171C (en) 1932-06-02 1933-05-27 Process for the preparation of light-sensitive photographic layers
GB15954/33A GB413853A (en) 1932-06-02 1933-06-02 Improvements in sensitive layers for photographic printing processes
FR756426D FR756426A (en) 1932-06-02 1933-06-02 Improvements in photographic copying processes and products used in this process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US615034A US1962307A (en) 1932-06-02 1932-06-02 Photographically sensitive element

Publications (1)

Publication Number Publication Date
US1962307A true US1962307A (en) 1934-06-12

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US (1) US1962307A (en)
DE (1) DE608171C (en)
FR (1) FR756426A (en)
GB (1) GB413853A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236651A (en) * 1964-02-24 1966-02-22 Alvin M Marks Photothermotropic compositions containing ligands and processes for utilizing same
US4045221A (en) * 1975-09-08 1977-08-30 Eastman Kodak Company Process of amplifying image in image recording layer by releasing reactant from image forming layer containing cobalt(III)complex
US4061497A (en) * 1975-07-14 1977-12-06 Eastman Kodak Company Catalytic activation of cobalt complex imaging by cobalt
US4171221A (en) * 1975-09-08 1979-10-16 Eastman Kodak Company High gain Co(III)complex imaging
US4188217A (en) * 1975-07-14 1980-02-12 Eastman Kodak Company Catalytic activation of cobalt complex imaging by cobalt sulfide
US4195998A (en) * 1974-04-15 1980-04-01 Eastman Kodak Company CO(III) Complex containing radiation sensitive element with diazo recording layer
US4201588A (en) * 1974-04-15 1980-05-06 Eastman Kodak Company Radiation sensitive co(III)complex photoreduction element with image recording layer
US4314019A (en) * 1976-09-07 1982-02-02 Eastman Kodak Company Transition metal photoreduction systems and processes
US4383029A (en) * 1979-08-16 1983-05-10 Matsushita Electric Industrial Co., Ltd. Recording medium and recording system

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE471336A (en) * 1946-04-13

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236651A (en) * 1964-02-24 1966-02-22 Alvin M Marks Photothermotropic compositions containing ligands and processes for utilizing same
US4195998A (en) * 1974-04-15 1980-04-01 Eastman Kodak Company CO(III) Complex containing radiation sensitive element with diazo recording layer
US4201588A (en) * 1974-04-15 1980-05-06 Eastman Kodak Company Radiation sensitive co(III)complex photoreduction element with image recording layer
US4061497A (en) * 1975-07-14 1977-12-06 Eastman Kodak Company Catalytic activation of cobalt complex imaging by cobalt
US4188217A (en) * 1975-07-14 1980-02-12 Eastman Kodak Company Catalytic activation of cobalt complex imaging by cobalt sulfide
US4045221A (en) * 1975-09-08 1977-08-30 Eastman Kodak Company Process of amplifying image in image recording layer by releasing reactant from image forming layer containing cobalt(III)complex
US4171221A (en) * 1975-09-08 1979-10-16 Eastman Kodak Company High gain Co(III)complex imaging
US4314019A (en) * 1976-09-07 1982-02-02 Eastman Kodak Company Transition metal photoreduction systems and processes
US4383029A (en) * 1979-08-16 1983-05-10 Matsushita Electric Industrial Co., Ltd. Recording medium and recording system

Also Published As

Publication number Publication date
FR756426A (en) 1933-12-09
DE608171C (en) 1935-01-17
GB413853A (en) 1934-07-26

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