US2305169A - Process of producing sensitive silver halide-colloidal aggregates - Google Patents

Process of producing sensitive silver halide-colloidal aggregates Download PDF

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US2305169A
US2305169A US194469A US19446938A US2305169A US 2305169 A US2305169 A US 2305169A US 194469 A US194469 A US 194469A US 19446938 A US19446938 A US 19446938A US 2305169 A US2305169 A US 2305169A
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silver
colloid
bromide
silver halide
cellulose
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US194469A
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Lierg Friedrich
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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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/496—Binder-free compositions, e.g. evaporated

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  • Sensitive silver halide emulsions are produced practically exclusively by gelatine solutions, -al though attempts have been made to substitute another colloid as carrying and protecting colloid for the silver halide for the gelatine, which is not of uniform nature and therefore varyingly influences the preparation of the silver halide emulsion.
  • the addition of the silver halide to the carrier colloid is carrid out in accordance with certain rules and precriptions determined in accordance with the latter in order to produce sensitive i'llms without layer, so that silver halide colloid aggregates exactly of the desired sensitiveness and characteristic of graduation are produced.
  • use is made of the colloid-chemical nature of the carrier colloid as well as of the silver halide in its nascent state e. g. differently from all known processes it places in reaction the carrier colloid when forming the silver halide in the carrier colloid by utilising-its electropolarity and that of the silver halide in the nascent state or by artificially producing the same.
  • the following rules have to be followed during the silver halide precipitation within the carrier colloid for the systematic constitution of a sensitive silver halide colloid aggregate of exactly determined characteristics.
  • a cellulose hydrate layer produced for instance from an acetyl lm by alkaline saponiflcation, is imbibed with a silver nitrate solution and if after its desiccation it is treated in the dark in a solution of bromides, there will take place silver bromide precipitations within the cellulose hydrate layer as carrier colloid, just in the same way as if a solution of bromides is used as rst imbibition bath andhereafter treatment is effected in the silver nitrate bath, whereby the quantity of the silver bromide introduced development-proof in the unexposed condition as well as its other characteristics depend on the electropolaric characteristic of the carrier colloid.
  • the silver bromide can be introduced only under certain conditions, which will be described hereinafter. That silver bromide, which has been formed by the flrst imbibition. of the silver nitrate solution and the subsequent treatment in a solution of 'bromides, always showed a very small sensitiveness, which reminded one of the sensitiveness of a Lippmann silver bromide emulsion, while the silver bromide produced by the treatment in a solution of bromides and the subsequent treatment in a silver salt bath is considerably darker in colour although it is'imbibed quite transparently and is very sensitive. As mentioned, the carrier colloid was of considerable influence even after the silver bromide substitution because.
  • the saponifled layer is not very capable of absorbing silver bromide which is development-proof (i. e. proof against blackening by a developer in non-actinic light). e. g. which is combined with the carrier colloid, as it will be explained hereinafter, while considerable quantities of development-proof silver bromide could be introduced in the event of concentrated saponication potassium hydroxide, which needs a short duration of action until the same degree of saponication is reached.
  • the phenomenon involved is believed to be a case of a colloid-chemical polarity.
  • the silver bromide is produced in the disacetylated acetyl cellulose by subsequent treatment in a solution of silver salt, e. g. if by the presence of the silver salt in excess the silver bromide is charged positively which in the nascent state always is of colloidal nature, the negative diacetylated acetyl cellulose does not react as a protective colloid, but an electrosorption takes place in view of the compensation of the opposite charges.
  • electrosorption it is to be understood the combination of two colloids of opposite electric charges. As is known, this compensation of opposite charges leads to coagulation in the case of liquid colloids which,
  • gelatine emulsion the only technically important difference being, that the silver bromide substituted in the diacetylated acetyl cellulose resu1ts,
  • Cellophane shows the same characteristics as disacetylated acetyl cellulose but somewhat weaker which isquite obvious, because the regeneration of the cellulose from all ⁇ its esters (nitrofacetylxanthate) results in hydrate cellulose which, per se, embodies already .a structural negative polarity owing to the free OH groups present in the molecule.
  • the elimination by diffusion of the rst imbibed bromide in the after-bath of silver nitrate may be prevented by addition thereto a large quantity of alcohol and using for the rst imbibition a bromide, for instance cadmium bromide, which is diiiicultly soluble in methyl alcohol.
  • a bromide for instance cadmium bromide, which is diiiicultly soluble in methyl alcohol.
  • Organic halogen compounds which are capable, with silver salt, of
  • silver halide can also be employed in place of the hereinbefore mentioned inorganic water-soluble halogen compounds.
  • I'hese organic halogen compounds are preferably employed in a form having the maximum resistance to solution in water, and, being dissolved in organic solvents such as alcohol or the like, are imbibed in the cellulose-hydrate layer.
  • the silver nitrate is in this instance employed ina solution of nothing but water.
  • organic halogen-salt solutions particularly those whose water-solubility diiers from that of the silver salts, and which are therefore imbibed, by means of a volatile organic solvent, in the deacetylated acetyl cellulose.
  • the feature of the present invention il view of the exact knowledge of the colloidchem ical procedure taking place during the addition of silver halide to rigid colloids, renders it possible to place in reaction the carrier-colloid by the suitable selection of its polarized characteristic either artificially produced or influenced by convenient additions, just like the polarized characteristic of the silver halide may be determined by prescribed measures during its precipitation, so that by the precise selection of both polarities it is possible to obtain the carrier-colloid adapted to the exact characteristics of an exactly con..
  • acetyl cellulose film is saponified in a bath of 1 part in volume of potassium hydroxide of 40 B., 1/2 part in volume of alcohol and 2 parts in volume of Water, hereafter the same is well washed for minutes. Now the film is dipped into a potassium bromide solution of 10%, the excess is drained off and dried.
  • potassium bromide also bromides which are of different solubility with respect to the silver salt may be added to the deacetylated acetyl cellulose. If necessary, the halogen salt after drying may be homogenised in a steam chamber.
  • the saponiiied acetyl cellulose impregnated with potassium bromide is immersed in a silver bath in the dark, that is to say, as photographers will know, in non-actinic light, which consists of a silver nitrate solution of 7.5% to which are added, for every 100 cc., 13.5 ccm. ammonia (specific Weight 0.91) and 200 to 500 cc. of methyl alcohol.
  • This mixture will be recognized by chemists as an alcoholic solution of ammoniacal silver nitrate, and reference to any chemical handbook containing tables of solubility will disclose that potassium bromide is only slightly soluble in alcohol. After the treatment in this solution of approximately one minute, the film thus prepared is washed for 2 hours.
  • the silver halide colloid aggregates produced in the manner hereinbefore described may be treated in the dry condition without that fogging, decomposition, insufficient absorption of the developer and like drawbacks may arise.
  • Fig. 5 illustrates a rigid or flexible carrier I3 of any convenient material, provided with a cellulose ester coat Il, and a hydrate layer I2 as shown in Fig. 2, the layer I2 being impregnated with a silver halide.
  • a process of producing a sensitive grainless silver bromide layer, proof againstl blackening by a photographic developer in non-actinic light comprises in subjecting at least one surface of an acetyl cellulose lm to a bath comprising by volume:
  • the acetyl cellulose may be spread or sprayed onto the desired base in the nature of a liquid cellone varnish and may be deacetylated after drying and the silver bromide may be substituted; or from the outlet, thin sensitive silver bromide Cellophane sheets are produced which are applied to plate-glass or metal plates which', owing to the said pressure and heatresistance of the sensitive silver bromide cellulose hydrate, may be effected by calendering in a dry or warm state by 'means of a fusing agent.
  • Grainless silver halide is introduced by electrosorption into the transformed surface layer, the halide being indicated by the stippling.
  • Fig. 3 shows a. cellulose ester sheet Il, both ed portion with potassium bromide by immersing it in a ten per cent solution of that salt, then draining and drying the film and subjecting it to a bath having the following proportionate composition: i
  • a process of producing photographic films by successively impregnating the carrier colloid with halogen salts and silver salts consisting in impregnating a cellulose hydrate lm with water soluble inorganic halides, drying the lm and then treating the film with a. silver nitrate bath containing at least a double quantity of an organic solvent in which the inorganic halogen compound employed is difllcultly soluble in order to obtain a complete formation of the silver halide Within the film or layer.
  • a process of producing photographic films by successively impregnating the carrier colloid with halogenV salts and silver salts, consisting in impregnating a cellulose hydrate film with Water soluble inorganic halide selected from the group consisting of cadmium bromide and zinc bromide which is adsorptively. combined with the cellulosehydrate film, drying the nlm and treating the film with a silver salt bath containing at least a double quantity of an organic solvent for completing formation of the silver halide within the nlm or layer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US194469A 1937-03-16 1938-03-07 Process of producing sensitive silver halide-colloidal aggregates Expired - Lifetime US2305169A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2596713A (en) * 1949-02-09 1952-05-13 Eastman Kodak Co Antihalation layer for cellulose ester lithographic printing plates
US2704262A (en) * 1950-06-06 1955-03-15 Hartford Nat Bank & Trust Co Method of superficially saponifying a cellulose ester film
US3779775A (en) * 1969-11-26 1973-12-18 Fuji Photo Film Co Ltd Light-sensitive materials

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2596713A (en) * 1949-02-09 1952-05-13 Eastman Kodak Co Antihalation layer for cellulose ester lithographic printing plates
US2704262A (en) * 1950-06-06 1955-03-15 Hartford Nat Bank & Trust Co Method of superficially saponifying a cellulose ester film
US3779775A (en) * 1969-11-26 1973-12-18 Fuji Photo Film Co Ltd Light-sensitive materials

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