Classifications

• • 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
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

• a photographic silver halide light-sensitive element comprising a support having thereon at least one layer containing a silver halide, wherein one colloid containing layer of said element contains: a) a compound of the formula M10 0r M10 wherein M is a hydrogen atom, an alkaline metal atom or ammonium group, and b) at least one of the following: unsubstituted benzenesulfinic acid, substituted benezenesulfinic acid and salts thereof; This element exhibits a marked reduction in the amount of yellow fog which is formed after storage and/0r development.
• the present invention relates to a photographic silver halide light-sensitive element in which the formation of yellow fogs is reduced.
• An exposed photographic silver halide light-sensitive element is usually successively processed in a developing bath, a stopping bath and a fixing bath.
• a thiosulfate a solvent for a silver halide which is contained in the fixing bath, is frequently intermixed in a developer.
• a thiosulfate which is a solvent for a silver halide is sometimes incorporated in the monobath.
• yellow fogs in photographic silver halide light-sensitive elements are caused by fine silver particles or silver sulfide deposited in any water-permeable colloid layer used in forming the photographic silver halide light-sensitive elements, not generally in baryta layers or emulsion layers thereof, or in water-permeable papers.
• the reason for the formation of such yellow fogs is as follows:
• a photographic silver halide light-sensitive element is processed in a developer containing a solvent for a silver halide, such as a thiosulfate, and when a material capable of forming a nucleus for reducing water-soluble silver ions to metallic silver, such as colloidal sulfur, silver or silver sulfide is present in a baryta layer or an emulsion layer thereof is present, water-soluble silver ions are reduced into metallic silver by reducing agents (for example a developing agent) in the developer, and these deposit on the aforesaid nuclei, thus forming the yellow fogs.
• reducing agents for example a developing agent
• the yellow fogs thus formed can be generally divided into two types, according to their method of formation.
• One method is where the formation of yellow fogs is observed when a photographic silver halide light-sensitive element is developed in a developer containing a solvent for silver halide, just after the preparation thereof.
• a second method is where the formation of yellow fogs is not observed when a photographic silver halide light-sensitive element is developed in a developercontaining a solvent for silver halide (just after the preparation thereof), but is observed when a photographic silver halide light-sensitive element is subjected to the same processing after it is stored under various conditions.
• the former is the situation when a material capable of being a nucleus for reducing water-soluble silver ions to metallic silver is already present in a baryta paper as a support for a photographic silver halide light-sensitive element, or else is present in a silver halide light-sensitive emulsion layer, a baryta paper, or a paper for a photographic silver halide lightsensitive element at the preparation thereof.
• the latter case is where a material capable of forming a nucleus for reducing water-soluble silver ions to metallic silver is formed in the emulsion layer, the baryta layer of the support of the photographic element, after it has been stored under various conditions.
• a photographic silver halide-sensitive element which contains at least one colloid layer which contains a compound capable of forming iodate ions will exhibit a marked reduction in the amount of yellow fogs which may be formed therein.
• benzenesulfinic acids and salts thereof may be added.
• Representative compounds capable of forming iodate ions are iodic acid, periodic acid and salts thereof.
• colloidal materials wherein the compound of the present invention may be incorporated include emulsion layers, protective layers and baryta layers.
• an object of this invention is to prevent the formation of yellow fogs in photographic silver halide light-sensitive elements, and in particular to prevent the formation of yellow fogs in photographic silver halide light-sensitive elements when they are stored or allowed to stand for long periods of time under various conditions.
• Another object of this invention is to provide a photographic silver halide light-sensitive element in which the formation of yellow fogs is effectively reduced or prevented.
• the colloid layers include every layer which contains colloidal materials for photographic silver halide light-sensitive elements, such as, emulsion layers, protective layers, and baryta layers.
• colloidal materials for photographic silver halide light-sensitive elements such as, emulsion layers, protective layers, and baryta layers.
• the factors which cause yellow fogs are, as mentioned above, due to the properties specific to the material which is used.
• lower molecular weight materials contained in a colloid layer or a paper base move freely through each layer when each colloid layer of the photographic silver halide light-sensitive element is swollen in a processing bath.
• the aforesaid material (such as an iodine compound, unsubstituted or substituted benzenesulfinic acid, or a salt thereof) may be effectively incorporated in any of the colloid layers and the paper base, and thus may, in effect, be incorporated in any layer in the present invention.
• a compound capable of forming iodate ions is generally a compound as iodic acid, periodic acid or a salt thereof, represented by M10, or MlO wherein M represents a hydrogen atom, an alkali metal or an ammonium group.
• M represents a hydrogen atom, an alkali metal or an ammonium group.
• ammonium iodate, iodic acid, sodium iodate, periodic acid, potassium periodate, ammonium periodate, and the like are examples of such compounds.
• the unsubstituted or substituted benzenesulfinic acids or salts thereof may generally be represented by the general formula:
• M represents a hydrogen atom, an alkali metal or ammonium group
• X represents hydrogen, a halogen atom, an alkyl group having 1-3 carbon atoms, or an amino group.
• Illustrative examples of such compounds are sodium benzenesulfinate, sodium p-toluenesulfinate, sodium pchlorobenzenesulfinate, and sodium p-aminobenzenesulfinate.
• the mechanism of the iodate compound of this invention for preventing the formation of yellow fogs has not yet been clarified, but the following is offered as a nonlimitative possible explanation.
• the yellow fogs form in the silver halide emulsion layer of a photographic silver halide light-sensitive element or at the interface between the silver halide emulsion layer and an adjacent layer thereof.
• the yellow fogs are considered to be formed through a stage where physical development nuclei are formed or present.
• yellowish developed silver as formed utilizing the physical development nuclei as the development nuclei when the photographic silver halide light-sensitive element is developed in a developing bath containing a solvent for a silver halide.
• the physical development nuclei as very fine particles of metallic silver (A,) formed in the silver halide emulsion layer or at the interface between the silver halide emulsion layer and a layer adjacent the silver halide emulsion layer, the nuclei being formed by the reduction of silver ions (Af).
• they may be considered as very fine particles of silver sulfide formed there by the reaction of silver ions (AJ) and a very small amount of a sulfur compound.
• the iodate will suppress the formation of metallic silver by oxidizing materials which will reduce silver ions
• the iodate compound will suppress the formation of silver sulfide by oxidizing the sulfur compound. Therefore, by incorporating the iodate compound in a photographic colloid layer of a photographic silver halide light-sensitive element the formation of the physical development nuclei will be suppressed, and the formation of yellow fogs can be reduced.
• the effect of the iodate compound can be prolonged for an even longer period of time. That is, after storing a photographic silver halide light-sensitive element containing an iodate compound therein for a long period of time, or else after allowing it to stand under conditions of high temperature and high humidity, the photographic light-sensitive element can be subjected to development, fixing, and washing as usual. It will then be observed that the unexposed portions of the photographic silver halide light-sensitive element become yellowish, caused perhaps by the spontaneous decomposition of the iodate compound.
• an iodate compound, M or MIC may be employed alone, or as a mixture of two or more types of such iodate compounds.
• an unsubstituted or benzenesulfinic acid, or a salt thereof may be used with the aforesaid iodate compound.
• the benzenesulfinic acid, or salt thereof may be used along, or as a mixture of two or more types thereof.
• the amount of the iodate compound is preferably about 0.5 g. per kilogram of silver halide emulsion (containing about 40 g. of silver halide).
• the aforesaid additives may be effectively added in any colloid layer of a photographic silver halide light-sensitive element and also they may be added in one colloid layer or two or more colloid layers. Furthermore, the additives may be incorporated in a colloid layer at any stage, but usually it is incorporated in a colloid, such as, a silver halide emulsion, a baryta coating composition, a dispersion for use as a protective layer, etc., at the preparation thereof, together with other additives, such as hardening agents, and wetting agents.
• a photographic silver halide light-sensitive element capable of providing sharp images having substantially no fogs or, at worst, very few fogs, is obtained.
• EXAMPLE 1 A baryta coating composition, containing a hardening agent, a wetting agent, etc., was applied to a paper in such proportions that the amounts of barium sulfate (anhydrous, gelatin, and sodium iodate (anhydrous) were 40 g., 4 g., and 0.05 g., respectively, per 1 square meter of the paper, to provide a baryta paper. Further, a photographic silver halide emulsion for photographic printing paper use was applied to the baryta layer thus formed to provide a photographic printing paper.
• a printing paper was prepared by the same procedure as above using the baryta coating composition containing no sodium iodate.
• the printing papers thus developed were fixed, washed and dried using standard techniques.
• EXAMPLE 2 A silver chlorobromide emulsion containing 50 mole percent silver bromide and 0.5 g. of sodium iodate (anhydrous) per kilogram of the silver halide emulsion (containing 50 g. of silver halide), with a dye sensitize-r, an antifoggant, a hardening agent, a wetting agent, etc., was applied to a baryta-coated paper to prepare a photographic printing paper. When the printing paper thus prepared was processed as in example 1, the formation of yellow fogs was negligible.
• EXAMPLE 3 A silver iodobromide emulsion containing 3 mole percent silver iodide and l g. of sodium iodate (anhydrous) per kilogram of the silver halide emulsion, together with a dye sensitizer, a hardening agent, a wetting agent, etc., was applied to a film base of triacetyl cellulose at a thickness of g./m. to provide a photographic silver halide light-sensitive film was prepared by the same procedure as above while using a silver halide emulsion having the same composition as above, with the exception that no sodium iodate was contained therein.
• EXAMPLE 4 A pure silver halide emulsion, containing 50 g. of silver chloride and 1.5 g. of sodium benzenesulfinate per kilogram of silver halide emulsion, together with a hardening agent, a wetting agent, and the like. was applied to a baryta-coated paper at a thickness of 50-80 g./m. To the emulsion layer thus formed there was applied, as a protective layer, an aqueous gelatin solution having the following composition:
• Gelatin 25 g. Sodium iodate (anhydrous) l g. Saponin (6% solution) 5 ml. Water 1,000 ml.
• a photographic silver halide light-sensitive element useful in preventing yellow fog comprising a support having thereon at least one layer containing a silver halide, and one colloid layer selected from the group consisting of a photographic silver halide emulsion layer and a layer adjacent to a silver halide emulsion layer, wherein said colloid layer of said element contains:
• b a member selected from the group consisting of unsubstituted benzenesulfinic acid, substituted benzenesulfinic acid, and salts thereof.

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

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Cited By (6)

• 1968
  • 1968-09-20 GB GB1227550D patent/GB1227550A/en not_active Expired
  • 1968-09-20 BE BE721222D patent/BE721222A/xx unknown
  • 1968-09-20 FR FR1586236D patent/FR1586236A/fr not_active Expired
  • 1968-09-23 US US761858A patent/US3615534A/en not_active Expired - Lifetime
  • 1968-09-23 DE DE1797383A patent/DE1797383C3/de not_active Expired

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