US3785823A - Polyhedral haloboranes as developer adjuvants with a polyethylene oxide condensation product - Google Patents

Polyhedral haloboranes as developer adjuvants with a polyethylene oxide condensation product Download PDF

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Publication number
US3785823A
US3785823A US00238480A US3785823DA US3785823A US 3785823 A US3785823 A US 3785823A US 00238480 A US00238480 A US 00238480A US 3785823D A US3785823D A US 3785823DA US 3785823 A US3785823 A US 3785823A
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United States
Prior art keywords
polyhedral
developer
haloborane
silver
polyethylene oxide
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Expired - Lifetime
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US00238480A
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English (en)
Inventor
J Bigelow
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • 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
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic 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
    • 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

  • ABSTRACT This invention relates to photographic films and developers and to improvement in film speed and top density which occurs by adding certain novel polyhedral haloborane compounds in synergistic combination with polyethylene oxide condenstaion products to the film-developer system. This invention also relates to improved developer tray life resulting from the use of these novel polyhedral haloboranes.
  • this invention comprises photosensitive silver halides dispersed in suitable binders such as gelatin which may be modified with certain other binding agents such as polyethylacrylate. These emulsions may also be further sensitized by the addition of gold and sulfur and after sensitization, coating and wetting aids and other adjuvants such as hardeners may also be added.
  • Polyethylene oxide condensation products are preferably added to the emulsion at this point, though they may be incorporated at any point during the emulsion making-preparation period. These polyethylene oxide condensation products are preferably added to the emulsion in the range of 0.0025 g to 2.0 g per 1.5 mole of silver halide.
  • a particularly useful polyethylene oxide condensation product is octylphenoxypolyethoxy ethanol added dissolved in water/alcohol mixtures at a preferred range of 0.01 g to 1.3 g of the polyethylene oxide condensation product per 1.5 mole of silver halide.
  • the emulsion is then coated on a suitable support such as polyethylene terephthalate and, after drying, overcoated with a thin stratum of gelatin which may be hardened to protect the emulsion during handling.
  • a suitable support such as polyethylene terephthalate
  • a thin stratum of gelatin which may be hardened to protect the emulsion during handling.
  • polyhedral haloborane compounds are borane polyhedrons, or fragments thereof containing 10 or 12 boron atoms interconnected to each other and preferably containing halogen atoms in place of most of the hydrogen substituents normally associated with polyhedral boranes.
  • the polyhedral haloboranes compounds are well described by Muetterties and Knoth in Polyhedral Boranes, Marcel Dekker, Inc., 1968.
  • a preferred cornpound ISHHZBJ-ZCWIHW' 7H O which may be added to the developer in Em range of .005 g to 1.5 g per liter of developer and in the preferred range of 0.1 g ,to 0.5 g per liter of developer.
  • emulsions having polyethylene oxide condensation products show a surprising and novel increase in speed and top density over the emulsions which do not contain the polyethylene oxide condensation product.
  • these polyhedral haloborane compounds are incorporated in common lith-type developers containing mainly hydroquinone as the sole developing agent, or substituted hydroquinones such as chloro, bromo or iodohydroquinone, or catechol or pyrogallol or others well known to those skilled in the art, the resulting film processed therein will, in comparison to films processed in lith-type developers without the polyhedral haloborane compounds of this invention, display some or all of the advantages of a shorter process time; higher speed; higher Dmax; longer developer tray life; the production of higher lith quality such as a shorter toe, more neutral color, improved dot" quality and longer halftone scale; lower developer sludge formation and resistance to aerial oxidation; and increased
  • the emulsions which may be used to practice this invention include all of the common silver halide types used, for example, in graphic arts, screened medical xray, industrial or nonscreened x-ray, negative cine or positive, color, etc. and may also include orthochromatic, panchromatic or infrared sensitizing dyes.
  • These aqueous silver halides include, for example, silver chloride, bromide, chloro-bromide, bromo-iodide, chloro-iodide or mixtures of chloride-iodide-bromide and also litho combinations having a majority of chloride with the rest being bromide alone or bromide with a small amount (generally less than percent) of iodide useful in lithographic films.
  • silver halides may be dispersed in gelatin or any other organic, macromolecular water permeable colloid, part or all of which may be replaced by synthetic agents, e.g., partially hydrolyzed polyvinyl acetates, polyvinyl ethers and acetals containing a number of extralinear Cl-l CH OH groups.
  • Other useful binders include hydrolyzed interpolymers of vinyl acetate and unsaturated addition polymerizable compounds such as maleic anhydride, acrylic and methacrylic acid, ethyl esters and styrene.
  • Suitable colloids of the last mentioned type are disclosed in U.S. Patents 2,276,322; 2,276,323; and 2,347,81 1.
  • the emulsions of this invention may be coated on any conventional photographic base or support such as glass, metal, various waterproof papers, cellulose derivatives, super polymers such as nylon, polyvinyl chloride, polystyrene.
  • any conventional photographic base or support such as glass, metal, various waterproof papers, cellulose derivatives, super polymers such as nylon, polyvinyl chloride, polystyrene.
  • the resulting film is preferably over-coated with a thin stratum of gelatin which may be hardened so as to protect the emulsion and improve the surface of the film.
  • This over-coating, or alternatively the emulsion underneath or the substratum anchoring layer or the anti-curling backing layer, may also contain certain adjuvants which are useful in preventing static.
  • Polyhedral haloboranes which can be used in practising this invention include the following:
  • polyethylene oxide condensation products may be used synergistically with the above polyhedral haloborane compounds of this invention to produce the novel results of this invention. Many of these are well described by Blake et al. in U.S. Pat. No. 2,400,532, 2,423,549 and 2,441,389.
  • Other suitable polyethylene oxide condensation products include:
  • EXAMPLE I A standard silver halide lithographic emulsion was prepared consisting of about mole percent of silver chloride and about 30 mole percent of silver bromide. This formulation is similar to that described by Nottorf in U.S. Pat. No. 3,142,568. The emulsion was dispersed in an aqueous gelatino-ethylacrylate binder and brought to its optimum sensitivity by the addition of gold and sulfur as well as being optically sensitized with an orthochromatic dye.
  • Step No. 11 of the 2 step wedge The improvement in speed and top density is appar ent from this example.
  • 0.01 g of polyhedral haloborane/liter of developer the toe portion of the H&D sensitometric curve is unusually shortened.
  • Useful maximum levels appear to be about 0.20 g.
  • EXAMPLE II An iodobromide emulsion consisting of 1.67 mole percent silver iodide and 98.33 mole percent silver bromide was precipitated in an alkaline medium, dispersed in gelatin and then brought to its optimum sensitivity with gold and sulfur. After cooling the emulsion the usual wetting agents, buffers and hardeners were added and the emulsion split into two portions. One portion was kept as control and to the other was added 0.5 g
  • Step 11 on the V 2 step index The synergistic effect of the polyhedral haloboranes of this invention in combination with polyethylene oxide condensation product is clearly shown in this example.
  • EXAMPLE III The emulsion described in Example II was prepared and split into two portions. To one portion was added 0.8 g of I-I,B, CI,,'7I-I,O per 1.5 moles of silver halide prior to coating and the other coated without the polyhedral haloborane. A polyethylene glycol condensate with an average molecular weight of 4000 was added to each portion at a level of 0.2 g/l .5 mole silver halide. Strips from the coatings were given the same exposure as those of Example 1 followed by development in the same developer with and without the polyhedral haloborane and the following results obtained:
  • Step No. 11 of the 2 wcdge From the above one can see that when adding polyhedral haloborane to either the emulsion or to the developer one obtains a useful advantage of speed, gradient and Dmax over adding polyethylene oxide condensation product by itself, without any deleterious increase in fog. If one adds the polyhedral haloborane to both emulsion and developer one can obtain a substantial increase in photographic speed but at some in-' crease in fog and decrease in gamma.
  • Example IV Sample strips of the coating prepared in Example I were given the same exposure and developed 2 minutes at 68F in the same developer composition of Example I except that various other polyhedral haloborane compounds were substituted at 0.2 g of compound/liter of developer as shown below. Results are also shown:
  • A-2, B, C and D contained 0.2 g H B CI flI-I O per 3.
  • the process of claim 2 in which said emulsion liter of developer with the following results: fo m a l r o a t,
  • each deoxide condensation product per 1.5 moles of silver halveloping solution was aged 40 minutes and was used to ide and said developer contains about 0.005 to 1.5 process 10 square feet of films plus six sensitometric grams of said polyhedral haloborane per liter of develstrips. Results follow: oper.
  • said developer contains, as the main developing agent, hydroquinone or substituted hydroquinones.
  • said silver halide is silver chloride, silver bromide, silver chlorobromide, silver bromo-iodide, silver chloro-iodide, mixtures of silver chloro-iodide-bromide or litho combinations.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00238480A 1972-03-27 1972-03-27 Polyhedral haloboranes as developer adjuvants with a polyethylene oxide condensation product Expired - Lifetime US3785823A (en)

Applications Claiming Priority (1)

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US23848072A 1972-03-27 1972-03-27

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US3785823A true US3785823A (en) 1974-01-15

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Country Status (5)

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US (1) US3785823A (enrdf_load_stackoverflow)
JP (1) JPS499236A (enrdf_load_stackoverflow)
BE (1) BE797303A (enrdf_load_stackoverflow)
DE (1) DE2314233A1 (enrdf_load_stackoverflow)
FR (1) FR2177971B3 (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209329A (en) * 1977-05-02 1980-06-24 E. I. Du Pont De Nemours And Company Low silver coating weight, high speed films having two similar emulsion layers
US4297441A (en) * 1979-06-28 1981-10-27 Konishiroku Photo Industry Co., Ltd. Photographic material
WO1995026354A1 (es) * 1994-03-25 1995-10-05 Centro Investigacion Justesa Imagen, S.A. Nuevos compuestos de boro iodados como agentes de contraste a los rayos x y composiciones farmaceuticas que los contienen
US6303284B1 (en) 2000-08-24 2001-10-16 Eastman Kodak Company Process for manufacture of photographic emulsion
US6326134B1 (en) 2000-08-24 2001-12-04 Eastman Kodak Company Process for manufacture of photographic emulsion

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209329A (en) * 1977-05-02 1980-06-24 E. I. Du Pont De Nemours And Company Low silver coating weight, high speed films having two similar emulsion layers
US4297441A (en) * 1979-06-28 1981-10-27 Konishiroku Photo Industry Co., Ltd. Photographic material
WO1995026354A1 (es) * 1994-03-25 1995-10-05 Centro Investigacion Justesa Imagen, S.A. Nuevos compuestos de boro iodados como agentes de contraste a los rayos x y composiciones farmaceuticas que los contienen
WO1995026353A1 (es) * 1994-03-25 1995-10-05 Centro Investigacion Justesa Imagen, S.A. Nuevos compuestos de boro iodados como agentes de contraste a los rayos x y composiciones farmaceuticas que los contienen
US6303284B1 (en) 2000-08-24 2001-10-16 Eastman Kodak Company Process for manufacture of photographic emulsion
US6326134B1 (en) 2000-08-24 2001-12-04 Eastman Kodak Company Process for manufacture of photographic emulsion

Also Published As

Publication number Publication date
JPS499236A (enrdf_load_stackoverflow) 1974-01-26
BE797303A (fr) 1973-09-26
FR2177971A1 (enrdf_load_stackoverflow) 1973-11-09
DE2314233A1 (de) 1973-10-18
FR2177971B3 (enrdf_load_stackoverflow) 1975-10-24

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