US3291608A - Enhanced activity of nuclei for physical development - Google Patents

Enhanced activity of nuclei for physical development Download PDF

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Publication number
US3291608A
US3291608A US342267A US34226764A US3291608A US 3291608 A US3291608 A US 3291608A US 342267 A US342267 A US 342267A US 34226764 A US34226764 A US 34226764A US 3291608 A US3291608 A US 3291608A
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United States
Prior art keywords
nuclei
physical development
gelatin
chloranil
photographic
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Expired - Lifetime
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US342267A
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Herbert S Elins
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US342267A priority Critical patent/US3291608A/en
Priority to DEE28504A priority patent/DE1295366B/en
Priority to GB3808/65A priority patent/GB1095893A/en
Priority to FR4059A priority patent/FR1423375A/en
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Publication of US3291608A publication Critical patent/US3291608A/en
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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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485—Direct positive emulsions
    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/26—Image-receiving layers
    • G03C8/28—Image-receiving layers containing development nuclei or compounds forming such nuclei

Definitions

  • a physical developer is used containing a reducing agent, a soluble silver salt as a source of free silver ions, and other materials to adjust pH and silver ion concentration.
  • These solutions deposit silver upon nuclei which may be zinc sulfide, lead sulfide, nickel sulfide, silver selenide, colloidal gold, colloidal silver or the like.
  • prefixation physical development the silver halide is not dissolved out first but the developer solution contains a strong silver halide solvent such as sodium thiosulfate which dissolves the halide as development proceeds.
  • One object of my invention is to provide nuclei having enhanced activity in phyiscal development ope-rations. Another object of my invention is to provide a method of making zinc sulfides which are especially adapted for use in products intended for physical development. A further object of my invention is to provide photographic products intended for physical development in which sulfides of enhanced activity in accordance with the in vention are employed. Other objects of my invention will appear herein.
  • chloranil-m-odified gelatin may conveniently be carried out as follows: 250 grams of a 10% aqueous solution of bone gelatin was dissolved in 650 cc. of distilled water at 40 C. 5 grams of tetrachloorp benzoquinone was added to the gelatin solution and the mass was stirred for 4 hours at room temperature. The mass was filtered thereby giving a tunbid solution which was subjected to centrifuging. There was thus obtained a clear red gelatin solution which was decanted from the yellow residue present and the mass was made up with distilled water to a total volume of 900 cc.
  • the pH was adjusted to 12.0 with 6 N H 1
  • the free silver ion concentration was adjusted from a solution of Ag(S203)2E prepared from AgCl and N-a2S20s-5H2O.
  • the total silver ion concentration of the developer was 5 10- moles/l.
  • the following example illustrates the use of colloidal zins sulfide nuclei prepared in accordance with the invention in photographic products including a silver halide photographic emulsion.
  • a photographic product was obtained composed of a cellulose acetate support having there-on a layer of silver bromoiodide photographic emulsion coated at a coverage of mg. of silver and 230 mg. of gelatin per square foot, over which was applied a layer of colloidal zinc sulfide nuclei prepared in accordance with the invention which layer contained 0.2 mg. of zinc sulfide and 560 mg. of gelatin per square foot.
  • the described product was exposed in an Eastman 1B sensitometer for 1/100 of a second. It was developed in a developer having the following composition:
  • the product was subsequently rinsed, fixed for 2 minutes in a hypo fixing bath, washed and dried. It was found that a low constrast negative image was obtained in the exposed areas and a positive image was obtained in the unexposed areas which had considerably greater density than that produced by the use of zinc sulfide nuclei prepared in untreated gelatin. Greater differentiation was therefore obtained between the contiguous negative and positive images when nuclei dispersed in the chloranil-modified gelatin were utilized.
  • the invention although illustrated in connection with zinc sulfide nuclei is not restricted thereto.
  • Other phys ical development nuclei such as colloidal gold of silver, metallic sulfides, selenides or tellurides such as lead sulfide, nickel sulfide, colloidal silver selenide, colloidal silver telluride, or other metallic physical development nuclei mentioned in the prior art as useful for this purpose can be prepared and used either as the sole development nuclei or mixed with one another in accordance with the invention.
  • the colloidal metals may be prepared in the presence of a chloranil-modi-fied gelatin by the dextrin reduction method of preparation of Carey-Lea as described in C01- loida-l Elements, by Weiser, John Wiley and Sons, New York, New York, 1933, page 119.
  • Metallic as used herein refers to heavy metals and their salts such as are useful as physical development nuclei.
  • composition useful in preparing photographic products which comprises chloranil-modified gelatin containing, dispersed therein, metallic physical development nuclei formed in situ.
  • composition useful in preparing photographic products which comprises chloranil-modified gelatin containing, dispersed therein, zinc sulfide physical development nuclei formed in situ.
  • composition useful in preparing photographic products which comprises chloranil-modified gelatin containing, dispersed therein, clolloidal silver physical development nuclei formed in situ.
  • a method of preparing metallic physical develop ment nuclei which comprises preparing a dispersion in finely divided form resulting from introducing an aqueous soltution of zinc salt and an aqueous solution of a water-soluble sulfide into an aqueous solution of chloranil-rnodified gelatin.
  • a product useful in reproduction procedures com prising a support having thereon a layer containing a dispersion of metallic physical development nuclei in chloranil-modified gelatin and wherein said dispersion is obtained by preparing the metallic physical development nuclei in the chloranil-modified gelatin.
  • a product useful in reproduction procedures comprising a support having thereon a llayer containing 'a dispersion of zinc sulfide physical development nuclei in ghloranil-modified gelatin and wherein said dispersion obtained by preparing zinc sulfide in the chloranil-modified gelatin.
  • a product useful in reproduction procedures com prising a cellulose acetate support having thereon a layer containing a dispersion of zinc sulfide physical development nuclei in chloranil-rnodified gelatin and wherein said dispersion is obtained 'by preparing zinc sulfide in the chloranil-modified gelatin.
  • a photographic material comprising a support having thereon a layer of a silver halide photographic emulsion and a layer containing metallic physical development nuclei formed in situ in chloranil-rn-odifiedgelatin.
  • a photographic material comprising a support having thereon a layer of a silver halide photographic emulsion and a layer containing zinc sulfide physical development nuclei in chloranil-modified gelatin and wherein said zinc sulfide physical development nuclei are obtained by preparing zinc sulfide in the chloranil-modified gelatin.
  • a photographic develop-ment process wherein a photographic material comprising a support having thereon a layer of a silver halide photographic emulsion and a layer containing metallic physical development nuclei formed in situ in chloranil-modified gelatin is exposed and developed by a physical photographic developer.
  • a photographic development process wherein a photographic material comprising a support having thereon a layer of a silver halide photographic emulsion and a layer containing zinc sulfide physical development nuclei in chloranil-rnodified gelatin and wherein said zinc sulfide physical development nuclei are obtained by preparing zinc sulfide in the chloranil-rnodified gelatin is exposed and developed by a physical photographic developer.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

United States Patent 3,291,608 ENHANCED ACTIVITY OF NUCLEI FOR PHYSICAL DEVELOPMENT Herbert S. Elins, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Feb. 3, 1964, Ser. No. 342,267 11 Claims. (Cl. 96-66) This invention relates to physical development nuclei of enchanced activity and the use of these nuclei in preparing photographic products.
There are two basic methods for obtaining developed silver images, one of which is chemical or direct development and the second method is termed physical development. By the latter method a physical developer is used containing a reducing agent, a soluble silver salt as a source of free silver ions, and other materials to adjust pH and silver ion concentration. These solutions deposit silver upon nuclei which may be zinc sulfide, lead sulfide, nickel sulfide, silver selenide, colloidal gold, colloidal silver or the like. In a modified form of physical development referred to as prefixation physical development the silver halide is not dissolved out first but the developer solution contains a strong silver halide solvent such as sodium thiosulfate which dissolves the halide as development proceeds.
One object of my invention is to provide nuclei having enhanced activity in phyiscal development ope-rations. Another object of my invention is to provide a method of making zinc sulfides which are especially adapted for use in products intended for physical development. A further object of my invention is to provide photographic products intended for physical development in which sulfides of enhanced activity in accordance with the in vention are employed. Other objects of my invention will appear herein.
I have found that metallic physical developement nuclei prepared in the presence of a chloranil-modified gelatin exhibit superior properties when employed in physical development operations. The gelatin employed as the peptizing material in preparing these nuclei is formed by adding tetrach-loro-p-benzoquinone (chloranil) to an aque ous solution of gelatin whereupon modification of the gelatin occurs. The thus modified gelatin is then employed as the peptizin-g material for various metallic physical development nuclei.
The preparation of chloranil-m-odified gelatin may conveniently be carried out as follows: 250 grams of a 10% aqueous solution of bone gelatin was dissolved in 650 cc. of distilled water at 40 C. 5 grams of tetrachloorp benzoquinone was added to the gelatin solution and the mass was stirred for 4 hours at room temperature. The mass was filtered thereby giving a tunbid solution which was subjected to centrifuging. There was thus obtained a clear red gelatin solution which was decanted from the yellow residue present and the mass was made up with distilled water to a total volume of 900 cc.
For nuclei in physical development operations metallic nuclei have been suggested, some of which are more useful for this purpose than others. The following description of preparing zinc sulfide may be followed in the making of other metallic physical development nuclei useful in photographic products. The solution of chloranil-modified gelatin obtained as described above at 40 C. was mixed with a solution of 1.26 grams anhydrous sodium sulfite in 74 cc. distilled water and then with 2.65 cc. of 0.944 Normal Na s. Immediately after mixing in the sodium sulfide a solution of 2.60 cc. of 0.99 Normal zinc nitrate in 270 cc. of distilled water was run into the mass while stirring over a period of 4 minutes, 35 seconds. There was thus formed a sol of zinc sulfide 3,291,608 Patented Dec. 13, 1966 4-amino-3-methyl-N-ethyl-N(beta-hydroxyethyl)aniline /2H SO -H O grams 1.274 K PO -H O do 50.0 [Ag-H moles 1X 10- Distilled water to make 1000 cc.
The pH was adjusted to 12.0 with 6 N H 1 The free silver ion concentration was adjusted from a solution of Ag(S203)2E prepared from AgCl and N-a2S20s-5H2O. The total silver ion concentration of the developer was 5 10- moles/l.
It was found that by the use of zinc sulfide nuclei prepared in chlorani-l-modified gelatin more active centers for physical development result than in the case of like products in which the zinc sulfide is prepared in an untreated gelatin.
The following example illustrates the use of colloidal zins sulfide nuclei prepared in accordance with the invention in photographic products including a silver halide photographic emulsion. A photographic product was obtained composed of a cellulose acetate support having there-on a layer of silver bromoiodide photographic emulsion coated at a coverage of mg. of silver and 230 mg. of gelatin per square foot, over which was applied a layer of colloidal zinc sulfide nuclei prepared in accordance with the invention which layer contained 0.2 mg. of zinc sulfide and 560 mg. of gelatin per square foot. The described product was exposed in an Eastman 1B sensitometer for 1/100 of a second. It was developed in a developer having the following composition:
Water to make 1.0 liter.
The product was subsequently rinsed, fixed for 2 minutes in a hypo fixing bath, washed and dried. It was found that a low constrast negative image was obtained in the exposed areas and a positive image was obtained in the unexposed areas which had considerably greater density than that produced by the use of zinc sulfide nuclei prepared in untreated gelatin. Greater differentiation was therefore obtained between the contiguous negative and positive images when nuclei dispersed in the chloranil-modified gelatin were utilized.
In other cases zinc sulfide nuclei were incorporated directly in silver halide emulsion layers rather than in a separate layer. In those cases the zinc sulfide prepared in chloranil-modified gelatin produced higher density positive images in the unexposed areas than were untreated gelatin was employed. This is also true in products adapted for use in silver halide dilfusion transfer processes such as in the type described in US. Patent No. 3,020,155 in that more active physical development was observed than is found where untreated gelatin is employed.
The invention although illustrated in connection with zinc sulfide nuclei is not restricted thereto. Other phys ical development nuclei such as colloidal gold of silver, metallic sulfides, selenides or tellurides such as lead sulfide, nickel sulfide, colloidal silver selenide, colloidal silver telluride, or other metallic physical development nuclei mentioned in the prior art as useful for this purpose can be prepared and used either as the sole development nuclei or mixed with one another in accordance with the invention.
The colloidal metals may be prepared in the presence of a chloranil-modi-fied gelatin by the dextrin reduction method of preparation of Carey-Lea as described in C01- loida-l Elements, by Weiser, John Wiley and Sons, New York, New York, 1933, page 119. Metallic as used herein refers to heavy metals and their salts such as are useful as physical development nuclei.
The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be eifected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
I claim:
1. A composition useful in preparing photographic products which comprises chloranil-modified gelatin containing, dispersed therein, metallic physical development nuclei formed in situ.
2. A composition useful in preparing photographic products which comprises chloranil-modified gelatin containing, dispersed therein, zinc sulfide physical development nuclei formed in situ.
3. A composition useful in preparing photographic products which comprises chloranil-modified gelatin containing, dispersed therein, clolloidal silver physical development nuclei formed in situ.
4. A method of preparing metallic physical develop ment nuclei which comprises preparing a dispersion in finely divided form resulting from introducing an aqueous soltution of zinc salt and an aqueous solution of a water-soluble sulfide into an aqueous solution of chloranil-rnodified gelatin.
5. A product useful in reproduction procedures com prising a support having thereon a layer containing a dispersion of metallic physical development nuclei in chloranil-modified gelatin and wherein said dispersion is obtained by preparing the metallic physical development nuclei in the chloranil-modified gelatin.
6. A product useful in reproduction procedures comprising a support having thereon a llayer containing 'a dispersion of zinc sulfide physical development nuclei in ghloranil-modified gelatin and wherein said dispersion obtained by preparing zinc sulfide in the chloranil-modified gelatin.
7. A product useful in reproduction procedures com prising a cellulose acetate support having thereon a layer containing a dispersion of zinc sulfide physical development nuclei in chloranil-rnodified gelatin and wherein said dispersion is obtained 'by preparing zinc sulfide in the chloranil-modified gelatin.
8. A photographic material comprising a support having thereon a layer of a silver halide photographic emulsion and a layer containing metallic physical development nuclei formed in situ in chloranil-rn-odifiedgelatin.
9. A photographic material comprising a support having thereon a layer of a silver halide photographic emulsion and a layer containing zinc sulfide physical development nuclei in chloranil-modified gelatin and wherein said zinc sulfide physical development nuclei are obtained by preparing zinc sulfide in the chloranil-modified gelatin.
1!). A photographic develop-ment process wherein a photographic material comprising a support having thereon a layer of a silver halide photographic emulsion and a layer containing metallic physical development nuclei formed in situ in chloranil-modified gelatin is exposed and developed by a physical photographic developer.
11. A photographic development process wherein a photographic material comprising a support having thereon a layer of a silver halide photographic emulsion and a layer containing zinc sulfide physical development nuclei in chloranil-rnodified gelatin and wherein said zinc sulfide physical development nuclei are obtained by preparing zinc sulfide in the chloranil-rnodified gelatin is exposed and developed by a physical photographic developer.
References Cited by the Examiner UNITED STATES PATENTS Re. 25,885 10/1965 Yackel et al. 96--76 X 2/ 1962 Yackel et al. 96-76 X OTHER REFERENCES NORMAN G. TORCHIN, Primary Examiner.
- C. E. DAVIS, Assistant Examiner.

Claims (1)

10. A PHOTOGRAPHIC DEVELOPMENT PROCESS WHEREIN A PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT HAVING THEREON A LAYER OF A SILVER HALIDE PHOTOGRAPHIC EMULSION AND A LAYER CONTAINING METALLIC PHYSICAL DEVELOPMENT NUCLEI FORMED IN SITU IN CHLORANIL-MODIFIED GELATIN IS EXPOSED AND DEVELOPED BY A PHYSICAL PHOTOGRAPHIC DEVELOPER.
US342267A 1964-02-03 1964-02-03 Enhanced activity of nuclei for physical development Expired - Lifetime US3291608A (en)

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US342267A US3291608A (en) 1964-02-03 1964-02-03 Enhanced activity of nuclei for physical development
DEE28504A DE1295366B (en) 1964-02-03 1965-01-14 Use of development nuclei made with modified gelatin for the physical development of silver images
GB3808/65A GB1095893A (en) 1964-02-03 1965-01-28 Photographic reproduction processes and materials therefor
FR4059A FR1423375A (en) 1964-02-03 1965-02-02 Process for preparing metallic seeds of physical development, new composition obtained and its applications

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607276A (en) * 1967-02-14 1971-09-21 Fuji Photo Film Co Ltd Process for making metal-glossy images and projection using the same
US3649275A (en) * 1969-09-02 1972-03-14 Eastman Kodak Co Photographic elements and processes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3020155A (en) * 1956-05-23 1962-02-06 Eastman Kodak Co Photographic diffusion transfer process
USRE25885E (en) * 1965-10-19 Silver halide sensitized lithographic printing plate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE25885E (en) * 1965-10-19 Silver halide sensitized lithographic printing plate
US3020155A (en) * 1956-05-23 1962-02-06 Eastman Kodak Co Photographic diffusion transfer process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607276A (en) * 1967-02-14 1971-09-21 Fuji Photo Film Co Ltd Process for making metal-glossy images and projection using the same
US3649275A (en) * 1969-09-02 1972-03-14 Eastman Kodak Co Photographic elements and processes

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GB1095893A (en) 1967-12-20
DE1295366B (en) 1969-05-14

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