US3155516A - Photographic products - Google Patents

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Publication number
US3155516A
US3155516A US236418A US23641862A US3155516A US 3155516 A US3155516 A US 3155516A US 236418 A US236418 A US 236418A US 23641862 A US23641862 A US 23641862A US 3155516 A US3155516 A US 3155516A
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United States
Prior art keywords
silver halide
silver
dispersion
organic
mercaptan
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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
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US236418A
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English (en)
Inventor
Blake Ralph Kingsley
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Priority to FR89467D priority Critical patent/FR89467E/fr
Priority to FR88737D priority patent/FR88737E/fr
Priority to NL134365D priority patent/NL134365C/xx
Priority to US236418A priority patent/US3155516A/en
Priority to US236420A priority patent/US3155507A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US236417A priority patent/US3155515A/en
Priority to US236412A priority patent/US3155514A/en
Priority to DEP30723A priority patent/DE1226877B/de
Priority to DEP30721A priority patent/DE1261397B/de
Priority to GB46344/62A priority patent/GB1031902A/en
Priority to GB46345/62A priority patent/GB1031903A/en
Priority to US317824A priority patent/US3155519A/en
Priority claimed from NL6408533A external-priority patent/NL6408533A/xx
Priority to NL6408533A priority patent/NL6408533A/xx
Priority to BE651688A priority patent/BE651688A/fr
Priority to US388919A priority patent/US3418124A/en
Priority to DK395464A priority patent/DK119392B/da
Priority to US390460A priority patent/US3384485A/en
Priority to CH1270464A priority patent/CH486719A/de
Priority to US403661A priority patent/US3284206A/en
Publication of US3155516A publication Critical patent/US3155516A/en
Application granted granted Critical
Priority to DEP37430A priority patent/DE1294186B/de
Priority to BE668111D priority patent/BE668111A/xx
Priority to GB34231/65A priority patent/GB1111226A/en
Priority to DEP37479A priority patent/DE1293581B/de
Priority to BE670823D priority patent/BE670823A/xx
Priority to GB43289/65A priority patent/GB1124772A/en
Priority to DEP37856A priority patent/DE1293582B/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/10—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D293/12—Selenazoles; Hydrogenated selenazoles
    • 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
    • G03C1/492—Photosoluble emulsions

Definitions

  • the unreduced silver remaining after development has been removed by silver halide solvents or rendered insensitive or transparent by treatment with complexing agents.
  • Optional after-treatments include intensification and reduction, toning and tinting.
  • the primary or first step in image formation always has been based on the selective reduction step.
  • the objects of this invention are realized by new silver halide compositions and layers in which images are formed, after exposure to actinic radiation, by imagewise solution of the silver halide.
  • the residual silver halide image may then be converted to silver, dyed or toned images.
  • novel photographic compositions and silver halide layers of this invention comprise silver halide crystals which have been treated, in substantially greater than fog-inhibiting amounts, with an organic mercaptan containing 1-2 mercapto groups taken from the group consisting of alkyl mercaptans and organic mercaptans containing two mercaptan groups linked to carbon and having a molecular weight greater than 75.
  • organic mercaptan containing 1-2 mercapto groups taken from the group consisting of alkyl mercaptans and organic mercaptans containing two mercaptan groups linked to carbon and having a molecular weight greater than 75.
  • R is an alkyl radical of 3-20 carbons, preferably 3l2 carbons, and where R is a divalent organic radical.
  • the latter can be hydrocarbon radicals or such radicals substituted by alkyl, alkoxy, carboxylic, halogen and cyano groups.
  • the silver salts of these compounds are less soluble in water than untreated silver chloride. Tautomeric forms of the organic compound may result in different linkages for the hydrogen atom than shown in the formula, e.g.,
  • the compound, RSH or HSRSH is characterized in that when admixed with an aqueous silver halide dispersion it protects the silver halide crystals to such an extent that when a silver halide dispersion protected by said compound is treated with 10%, by weight,
  • the silver halide crystals are dispersed in a water-permeable organic colloid to form a light-sensitive photographic emulsion.
  • the selected aliphatic mercapto or dimercapto compound can be added to the silver halide emulsion while the latter is in the liquid state or the emulsion may be coated on a suitable support and the resulting element bathed or impregnated with a solution, e.g., an alcoholic solution of the organic compound.
  • the amount of organic compound in the silver halide emulsion is from about 0.125 to 314 g. per mole of silver halide but wider ranges of concentration can be useful, depending upon the particular organic compound, the size and nature of the silver halide crystals, the presence of other materials which may partially cover the surface of the silver halide crystal, and upon various other factors.
  • gelatin:silver halide ratio is quite flexible and may vary from 3:1 to 1:30 depending on the particular organic compound and application.
  • the silver halide is present in much higher concentra' tion than in conventional emulsions and emulsion layers.
  • direct positive images can be formed by a process which comprises (a) Exposing imagewise to actinic light a photo-sensitive layer comprising silver halide crystals treated with the organic compound as described above,
  • the silver halide image may be viewed directly, e.g., by projection (if on a transparent support) or it may be intensified by (d) Converting the residual silver halide to silver by treatment in a fogging developer, e.g., a high pH, l-phen yl-4-methyl-3-pyrazolidone/hydroquinone developer containing iodide ion or by fogging the emulsion by exposure to light and then treating with a silver halide reducing agent, e.g., a conventional silver halide developer, and
  • a fogging developer e.g., a high pH, l-phen yl-4-methyl-3-pyrazolidone/hydroquinone developer containing iodide ion
  • a silver halide reducing agent e.g., a conventional silver halide developer
  • the imagewise solution of the exposed silver halide/organic compound stratum may be effected by the silver halide solvent commonly used as photographic fixing agents, e.g., sodium thiosulfate, sodium thiocyanate, concentrated solutions of potassium bromide, etc.
  • Reduction of the treated, residual silver halide may be accomplished by use of any chemical reducing agent capable of reducing silver ion to silver metal, e.g., hydroquinone, metol, sodium hydrosulfite and stannous chloride.
  • the function of the reducing agent may be enhanced by modifying the surface properties of the treated, residual silver halide crystals by means of alcohol, thiourea, potassium iodide, etc
  • the silver halide image may be toned, e.g., with sodium sulfide, sodium selenide, etc.
  • color images may be obtained by developing the treated, residual silver halide with a primary aromatic amine color developing agent in the presence of a color coupling compound either in the developing bath or previously incorporated in the emulsion.
  • the candidate aliphatic mercapto or dimercapto compound must render a dispersion of silver halide crystals insoluble in a silver halide solvent, i.e., an aqueous solution of sodium thiosulfate, at some pH between 1 and 13. If the candidate compound effects the insolubility required of Test A, it must also, to have utility, pass Test B by forming with said dispersion of silver halide crystals a reaction product which, upon treat ment with an aqueous solution of sodium hypochlorite, becomes soluble when subsequently treated with aqueous sodium thiosulfate.
  • a silver halide solvent i.e., an aqueous solution of sodium thiosulfate
  • a solution nearly saturated at 25 C. with a candidate organic compound is prepared using ethanol, acetone, dimethyl formamide, water or other suitable solvents. Depending on the solubility, a solution concentration from 0.01 to percent by weight is obtained. Twenty-five ml. of a silver chlorobrornide dispersion containing mg. of silver halide (calculated as silver bromide), prepared as described below, is treated with small increments (i.e., about 0.1 to 0.2 ml.
  • This test may be repeated for various pH increments from 1 to 13. Although there is some optimum pH value at which the test is most sensitive, this is not a sharp maximum which must be precisely attained. Rather, it has been found that there is a fairly broad range of pH values (e.g., 2.0 to 3.0 pH units) over which the test has a satisfactory sensitivity.
  • the silver halide dispersion might be tested without adjustment (e.g., at pH 5.0 to 7.0) and if insolubilization occurs here, Test A is completed. If there is no insolubilization, the test is repeated at a higher pH (e.g., about 11-13).
  • TEST B An organic compound capable of insolubilizing a silver halide dispersion according to Test A is now ready for the next test, which again will be conducted under safelight conditions.
  • To the above silver halide dispersion there is added the minimum amount of a solution of the candidate organic compound found necessary for insolubilization.
  • Half milliliter samples of the dispersion containing 0.5 mg. of AgBr or 0.29 mg. Ag are placed in two test tubes. To one sample is added 0.5 ml. of water; to the other is added 0.5 ml. of a 5% by weight aqueous solution of sodium hypochlorite (containing 25 mg. sodium hypochlorite. Next, there is added to both samples, 1.0 ml.
  • Silver Halide Dispersion Preparati0lzDispersiolz I
  • the silver halide dispersion disclosed in Tests A and B is prepared according to the following specifications. In red light, 30 g. of photographic grade gelatin is soaked in 1100 ml. of distilled water for 10 minutes. The temperature is then raised to 120 F. and g. of solid ammonium chloride added. The mixture is stirred at F. and after the ammonium chloride is completely dissolved, a solution made by diluting 500 ml. of 3 N silver nitrate with 2000 ml. of distilled water is added while stirring the solution for 5 seconds. This mixture is held at 120 F. for 4 minutes with stirring, and then ml.
  • This mixture is vigorously stirred for 10 minutes at 95 F. and then the pH adjusted to 6.1i0.1 with aqueous sodium hydroxide solution.
  • the redispersed emulsion is then analyzed for silver halide content calculated as silver bromide and a dispersion made by diluting the appropriate amount with distilled water such that the dispersion contains 1 mg. calculated silver bromide per ml.
  • Particularly preferred organic compounds of the formulae wherein R is a monovalent aliphatic radical and R is a divalent organic radical are those which form silver salts of the formulae
  • the useful silver salts of the above formula are those which are said salts being insoluble in aqueous ammonium hydroxide at pH 12.
  • Dispersed crystals of silver halide, treated with a suitable organic compound of one of the above formulae, are affected by exposure of a portion of said crystals to actinic radiation, e.g., ultraviolet, visible, infrared, X- radiation, etc., to such an extent that at least 20% of the less soluble crystals remain after 90% of the more soluble crystals dissolve when treated in by weight aqueous sodium thiosulfate solution.
  • actinic radiation e.g., ultraviolet, visible, infrared, X- radiation, etc.
  • solubilizing groups in the R or R' portion of the above formulae should be avoided in order that reaction products with silver halide will be formed which will significantly reduce the solubility of silver halide grains in silver halide solvents.
  • the silver halide need not be a combination of silver chloride and silver bromide, but may be silver chloride, silver bromide and other mixed halide systems conventional in photographic practice, e.g., silver bromoiodide. While, for rapid processing, a high silver halide to binder ratio is preferred, more conventional ratios can also be used.
  • water-permeable organic colloid binding agents can be used and in some cases such binders can be used alone.
  • Such agents include water-permeable or water-soluble polyvinyl alcohol and its derivatives, e.g., partially hydrolyzed polyvinyl acetates, ethers and acetals containing a large number of intralinear CH -CHOH groups, hydrolyzed interpolymers of vinyl acetate and unsaturated addition polymerizable compounds such as maleic anhydride, acrylic and methacrylic acid esters and styrene. Suitable such colloids of the last-mentioned type are dis closed in US.
  • Patents 2,276,322; 2,276,323 and 2,397,866 The useful polyvinyl acetals include polyvinyl acetaldehyde acetal, poylvinyl butyraldehyde acetal and polyvinyl sodium o-sulfobenzaldehyde acetal.
  • Other useful colloid binding agents which can be used include the poly-N- vinyllactains of Bolton US. Patent 2,495,918, various polysaccharides, e.g., dextran, dextrin, etc., the hydrophilic copolymers in Shacklett US. Patent 2,833,650, hydrophilic cellulose ethers and esters, and polymers of acrylic and methacrylic esters and amides.
  • it has been found practical to treat silver halide layers on a base material in the essential absence of a binder e.g., by chemical or vacuum deposition.
  • the emulsions may optionally contain any of the usual adjuvants customarily employed in silver halide systems so long as they do not interfere with the adsorption and complexing action of the essential ingredient of the invention.
  • the emulsions can be coated on any suitable support, e.g., cellulose esters, cellulose mixed esters; superpolymers, e.g., polyvinyl chloride (co) vinyl acetate, polyvlnyl acetals, butyrals; polystyrene; polyarnides, e.g., polyhexamethylene adipamide, polyesters, e.g., polycarbonates, polyethylene terephthalate, polyethylene terephthalate/ isophthalate, esters formed by condensing terephthalic acid and its derivatives, e.g., dimethyl terephthalate with' propylene glycol, diethylene glycol, tetramethylene glycol, cyclohexane-1,4-dimethanol (hexahydro-p-xylene dialcohol); paper, metal, glass, etc.
  • suitable support e.g., cellulose esters, cellulose mixed esters; superpolymers, e.
  • the desirable concentration of the selected organic compound depends on many factors such as the size and solubility of the organic compound, the nature of its reaction with silver halide, the size and nature of the silver halide crystals, the presence of other materials which may react with or be adsorbed to the surface of the silver halide, etc.
  • Example III a number of organic compounds are disclosed which were tested in a dispersion of silver halide crystals wherein the average grain size was 035 (micron) in diameter, therefore about O.043 in volume, assuming cubic grains.
  • the silver halide comprised 70 mole percent silver chloride and 30 mole percent silver bromide, with a specific density of about 5.7 g./cc.
  • 157 g./mole+0.25 1t 6.3 10 grains/mole.
  • a particularly preferred aliphatic mercaptan is n-dodecyl mercaptan (or dodecanethiol). Assuming that a single molecule of the compound could occupy an area of thirty square angstroms, it would require 1.5 1O molecules to occupy a molar surface area of silver halide. With a molecular Weight of 202, this would require of n-dodecyl mercaptan to insolubilize one mole of the silver halide. As disclosed in Example IV in a photographic emulsion coated on a film base support it was found that 0.4 g. of n-dodecyl mercaptan per mole of silver halide gave optimum results. Thus the experimental values are in good agreement with the theoretically determined amount of n-dodecyl mercaptan required to cover the silver halide surface.
  • elements suitable for this novel process can be prepared by bathing a photographic film in a solution of an appropriate organic compound.
  • the silver halide crystals near the surface of the coated emulsion stratum are in contact with a higher concentration of the organic compound. Crystals farther from the surface, are treated with less of the organic compound and, if the rate of diffusion is sufiiciently slow, there may be considerably less of the organic compound (even approaching zero) reacting with the lower than with the surface silver halide crystals.
  • satisfactory results might be obtained with only a fraction, e.g., one-half, of the amount of the organic compound theoretically calculated as required to just cover the surface of a mole of the crystals.
  • a photographic element was prepared by coating an aqueous gelatin dispersion of silver chlorobromide (70 mole percent silver chloride and 30 mole percent silver bromide) on a film base prepared as described in Example IV of Alles US. Patent 2,779,684.
  • the dispersion had a ratio of silver halide to gelatin of 28:1 by weight and was coated at a pH of 6 at a rate of 116 milligrams of silver halide per square decimeter. After drying, the element was bathed for about 15 seconds in a dilute aqueous solution of n-dodecyl mercaptan having a pH of 5.1 and dried.
  • n-dodecyl mercaptan was prepared by diluting 5 m1. of a stock solution (1 gram of the compound made up to ml. in ethanol) with an additional 20 ml. of ethanol and 10 ml. of Water. The dried element was then exposed behind a photographic transparency for 15 seconds to the radiation from a General Electric 2A photoflood lamp at a distance of about 6l0 inches. The exposed element was then immersed in a 12.8% aqueous solution of sodium thiosulfate for 30 seconds resulting in removal of the silver salt in the exposed areas.
  • the fixed film was then rinsed briefly in water and bathed in a rapid acting fogging developer solution comprising l-phenyl- 4-methyl-3-pyrazolidone and hydroquinone as reducing agents to which there had been added potassium iodide and a direct positive image formed. All of the above operations were carried out in ordinary fluorescent room illumination.
  • the treated element is converted into an exact reproduction (i.e., direct positive image) of the original transparency. After brief washing in water and drying, it is satisfactory for use in any application where an exact reproduction is desired, e.g., in the graphic arts field, for a projection transparency, etc.
  • Example II Example I was repeated except that ethylcyclohexyl dimercaptan was substituted for the n-dodecyl mercaptan of that example and the exposed element was immersed in the 12.8% aqueous solution of sodium thiosulfate for only 10 seconds instead of 30 seconds. As in Example I, a direct positive image was obtained.
  • Test C a simulated photographic test was devised and will be designated as Test C. It is noted that there is complete testing correlation in that any compound which was found suitable according to the photographic test to be described in the next paragraph was also found suitable according to Tests A and B.
  • TEST C A 0.5 ml. portion of the insolubilized dispersion prepared in Test A under safelight conditions is placed in a 12 x 75 mm. Pyrex test tube three inches from a No. 2 reflcctoflood lamp. This insolubilized dispersion is exposed to the lamp for up to 10 minutes. A control consisting of another 0.5 ml. portion of the insolubilized silver halide dispersion from Test A is taken under safelight conditions. Two-tenths of a milliliter of 10% aqueous sodium thiosulfate is added to each of the dispersion samples taken and compared under safelight conditions. Any reduction in turbidity of the dispersion exposed to the refiectofiood lamp compared to the unexposed control after treatment with aqueous sodium thiosulfate solution shows that photosolubilization occurs.
  • Tests A, B and C were all conducted using Silver Halide Dispersion I, the preparation of which was given immediately following the description of the procedure for Test B.
  • the qualitative procedure of Test A was repeated in a more quantitative manner, using a ripened, washed and redispersed (but not chemically sensitized) gelatino-silver chlorobromide emulsion as described in Example I of assignees copending application, Nottorf, U.S. Serial No. 94,989, filed March 13, 1961.
  • Dispersion II This emulsion is designated in the table below as Dispersion II, and was made as follows: A lithographic emulsion having a silver halide composition of 30 mole percent AgBr and 70 mole percent AgCl and having 20 grams of gelatin present per mole of silver halide for the steps of precipitation and ripening was freed of unwanted, soluble, by-product salts by a coagulation and wash procedure as taught in Waller ct al. US. Patent 2,489,341, wherein the silver halide and most of the gelatin were coagulated by an anionic wetting agent, sodium lauryl sulfate, using an acid coagulation environment. Following the washing step, the emulsion coagulate was redispersed in water together with 47 grams of additional bulking gelatin.
  • EXAMPLE IV An emulsion as described in Dispersion II, Example HI, was redispersed in a gelatin solution which contained 47 g. gelatin per mole of the silver halide. A pH 6.01:1 was maintained While dispersing min. at 110 F. The emulsion was brought to 2320 g. by addition of Water and the temperature adjusted to 120 F. Fourtenths of a gram of n-dodecyl mercaptan was added per mole of silver halide from a 1% by weight ethanol solution. Chrome alum hardener was added and the emulsion was diluted with Water to a total weight of 2334 g. per mole of silver halide.
  • This emulsion was applied at a coating weight of 4-6 mg. of silver per square decimeter on 0.004 inch thick polyester photographic film base as described in Example I.
  • the coating after imagewise exposure, showed a greater rate of fixing in a 1.0 N (0.5 M) aqueous solution of sodium thiosulfate in exposed areas than in the unexposed areas so as to form a positive silver halide image.
  • Subsequent flashing to White light, followed by treatment with a reducing agent a conventional photographic developing solution containing 1- phenyl-4-methyl-3-pyrazolidone and hydroquinone
  • the optical densities of completely unexposed areas and heavily exposed areas of the film as determined using a Western Electric RA-lOO-C Densitometer, Were 0.21 and 0.10, respectively.
  • the silver halide photosoluble elements of this invention differ from conventional silver halide emulsions containing anti-fogging agents in that the insolubilizing compounds used in the photosoluble elements are present in substantially greater than fog-inhibiting amounts, the latter amounts being the maximum quantity which provides low fog Without serious loss in speed and photographic quality. For this reason it is not practical to use photosoluble elements in place or" ordinary silver halide photographic materials. When photosoluble elements are exposed and processed normally, development proceeds slowly and incompletely to give a negative silver image having much less speed and lower density. In addition,
  • novel photographic compositions of this invention have numerous advantages.
  • a primary advantage is the simplicity of their preparation. They can be exposed and processed to images under ordinary room light conditions.
  • the photographic processes applicable to the compositions and elements of the invention likewise have advantages over previously known systems based on selective reductions of exposed silver halide for forming either direct positive or negative images without resorting to the special effects and sensitizing procedures previously used for preparing such images.
  • this present process is not limited to the use of certain photographic developing agents but may be accomplished by using a Wide range of reducing agents. Many such compounds are of very low cost and can be used to form images of much higher covering power than customary, thus effect ing important economies in processing, as well as greatly increasing the efiiciency of the silver image With a resultant increase in sensitivity.
  • compositions and elements of this invention may be processed to form silver halide or silver images without the requirement of special equipment but instead conventional equipment and apparatus can be used.
  • a further advantage is that the processes can be carried out successfully by photographic technicians and photographers of ordinary skill.
  • a still further advantage is that the processes utilize conventional reducing agents, e.g., developers and fixing agents. Still additional advantages will be apparent from the above description of the invention.
  • a photographic silver halide composition before exposure to actinic radiation containing in greater than fog-inhibiting amounts an organic mercaptan containing 1-2 mercapto groups, having a molecular Weight greater than 75 and being taken from the group consisting of alkyl mercaptans and organic mercaptans containing two tercaptan groups linked to carbon, the silver mercaptide of said organic mercaptaue being of lower solubility in water than silver chloride; said organic mercaptan being present in such an amount, in terms of the ratio of its Weight to the surface area of the silver halide crystals, that when admixed in such ratio with an aqueous silver chlorobromide dispersion, 70/30 mole percent, gelatin dispersion containing 0.29 mg.
  • a photographic element beariiu a layer before exposure to actinic radiation comprising silver halide containing in greater than fog-inhibiting amounts an organic rnercaptan containing 1-2 mercapto groups, having a molecular weight greater than 75 and being taken from the group consisting of alkyl mercaptans and organic mercaptans containing two mercaptan groups linked to carbon, the silver salt of said organic mercaptan being of lower solubility in water than silver chloride; said organic mercaptan being present in such an amount, in terms of the ratio of its weight to the surface area of the silver halide crystals, that when admixed in such ratio with an aqueous silver chlorobromide dispersion, 70/30 mole percent, gelatin dispersion containing 0.29 mg.
  • organic mercaptan is an alkyl mercaptan of 3-12 carbon atoms.
  • said or- 2 ganic compound is an organic mercaptan containing two mercaptan groups linked to carbon.
  • a photographic silver halide emulsion before exposure to actinic radiation comprising silver halide cry-1; tals previously made less soluble in a silver halide solvent by treatment with 0.125 gram to 314 grams and substantially greater than fog-inhibiting amounts, per mole of silver halide, of an organic mercaptan containing l-2 mercapto groups, having a molecular weight greater than and being taken from the group consisting of alkyl mercaptans and organic mercaptans containing two mercaptan groups linked to carbon, the silver salt of said organic mercaptan being of lower solubility in water than silver chloride; said organic mercaptan being present in such an amount, in terms of the ratio of its weight to the surface area of the silver halide crystals, that when admixed in such ratio with an aqueous silver chlorobromide dispersion, 70/30 mole percent, gelatin dispersion containing 0.29 mg.
  • Keelan The Journal of Photographic Science, vol. 5, November 1, December 1957, pages 144 and 145.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (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)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US236418A 1961-12-08 1962-11-08 Photographic products Expired - Lifetime US3155516A (en)

Priority Applications (26)

Application Number Priority Date Filing Date Title
NL134365D NL134365C (enrdf_load_stackoverflow) 1961-12-08
FR89467D FR89467E (enrdf_load_stackoverflow) 1961-12-08
FR88737D FR88737E (enrdf_load_stackoverflow) 1961-12-08
US236420A US3155507A (en) 1961-12-08 1962-11-08 Photographic processes
US236418A US3155516A (en) 1961-12-08 1962-11-08 Photographic products
US236417A US3155515A (en) 1961-12-08 1962-11-08 Photographic products
US236412A US3155514A (en) 1961-12-08 1962-11-08 Photographic compositions and elements
DEP30723A DE1226877B (de) 1961-12-08 1962-12-07 Photographische Silberhalogenidemulsion
DEP30721A DE1261397B (de) 1961-12-08 1962-12-07 Photographisches Verfahren zur Herstellung positiver Bilder
GB46344/62A GB1031902A (en) 1961-12-08 1962-12-07 Improvements in silver halide photography
GB46345/62A GB1031903A (en) 1961-12-08 1962-12-07 Photographic silver halide materials and processes
US317824A US3155519A (en) 1961-12-08 1963-10-21 Photographic compositions, layers and elements
NL6408533A NL6408533A (enrdf_load_stackoverflow) 1961-12-08 1964-07-24
US388919A US3418124A (en) 1961-12-08 1964-08-11 High contrast direct positive by using active cations in silver halide solvent
BE651688A BE651688A (enrdf_load_stackoverflow) 1961-12-08 1964-08-11
DK395464A DK119392B (da) 1961-12-08 1964-08-11 Fotografisk sølvhalogenidmateriale til kopiering.
US390460A US3384485A (en) 1961-12-08 1964-08-18 Silver halide emulsions photosolubilized with optical sensitizing dyes and silver mercaptides
CH1270464A CH486719A (de) 1961-12-08 1964-09-30 Photographische Halogensilberemulsion und ihre Verwendung
US403661A US3284206A (en) 1961-12-08 1964-10-13 Image yielding layers
GB34231/65A GB1111226A (en) 1961-12-08 1965-08-10 Improvements relating to the production of images
DEP37430A DE1294186B (de) 1961-12-08 1965-08-10 Photographisches Verfahren zur Herstellung positiver Bilder
BE668111D BE668111A (enrdf_load_stackoverflow) 1961-12-08 1965-08-10
DEP37479A DE1293581B (de) 1961-12-08 1965-08-18 Photographische Silberhalogenidemulsion
BE670823D BE670823A (enrdf_load_stackoverflow) 1961-12-08 1965-10-12
GB43289/65A GB1124772A (en) 1961-12-08 1965-10-12 Improvements in silver halide photography
DEP37856A DE1293582B (de) 1961-12-08 1965-10-13 Photographische Silberhalogenidemulsion

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
US15813261A 1961-12-08 1961-12-08
US236418A US3155516A (en) 1961-12-08 1962-11-08 Photographic products
US236417A US3155515A (en) 1961-12-08 1962-11-08 Photographic products
US236420A US3155507A (en) 1961-12-08 1962-11-08 Photographic processes
US236412A US3155514A (en) 1961-12-08 1962-11-08 Photographic compositions and elements
US317824A US3155519A (en) 1961-12-08 1963-10-21 Photographic compositions, layers and elements
NL6408533A NL6408533A (enrdf_load_stackoverflow) 1961-12-08 1964-07-24
US388919A US3418124A (en) 1961-12-08 1964-08-11 High contrast direct positive by using active cations in silver halide solvent
US390460A US3384485A (en) 1961-12-08 1964-08-18 Silver halide emulsions photosolubilized with optical sensitizing dyes and silver mercaptides
US403661A US3284206A (en) 1961-12-08 1964-10-13 Image yielding layers

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US3155516A true US3155516A (en) 1964-11-03

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US236418A Expired - Lifetime US3155516A (en) 1961-12-08 1962-11-08 Photographic products
US236417A Expired - Lifetime US3155515A (en) 1961-12-08 1962-11-08 Photographic products
US236412A Expired - Lifetime US3155514A (en) 1961-12-08 1962-11-08 Photographic compositions and elements
US236420A Expired - Lifetime US3155507A (en) 1961-12-08 1962-11-08 Photographic processes
US317824A Expired - Lifetime US3155519A (en) 1961-12-08 1963-10-21 Photographic compositions, layers and elements
US388919A Expired - Lifetime US3418124A (en) 1961-12-08 1964-08-11 High contrast direct positive by using active cations in silver halide solvent
US390460A Expired - Lifetime US3384485A (en) 1961-12-08 1964-08-18 Silver halide emulsions photosolubilized with optical sensitizing dyes and silver mercaptides
US403661A Expired - Lifetime US3284206A (en) 1961-12-08 1964-10-13 Image yielding layers

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US236417A Expired - Lifetime US3155515A (en) 1961-12-08 1962-11-08 Photographic products
US236412A Expired - Lifetime US3155514A (en) 1961-12-08 1962-11-08 Photographic compositions and elements
US236420A Expired - Lifetime US3155507A (en) 1961-12-08 1962-11-08 Photographic processes
US317824A Expired - Lifetime US3155519A (en) 1961-12-08 1963-10-21 Photographic compositions, layers and elements
US388919A Expired - Lifetime US3418124A (en) 1961-12-08 1964-08-11 High contrast direct positive by using active cations in silver halide solvent
US390460A Expired - Lifetime US3384485A (en) 1961-12-08 1964-08-18 Silver halide emulsions photosolubilized with optical sensitizing dyes and silver mercaptides
US403661A Expired - Lifetime US3284206A (en) 1961-12-08 1964-10-13 Image yielding layers

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US (8) US3155516A (enrdf_load_stackoverflow)
BE (1) BE670823A (enrdf_load_stackoverflow)
DE (5) DE1261397B (enrdf_load_stackoverflow)
FR (1) FR89467E (enrdf_load_stackoverflow)
GB (4) GB1031903A (enrdf_load_stackoverflow)

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US3647439A (en) * 1968-10-01 1972-03-07 Eastman Kodak Co Photographic element, composition and process
US4014699A (en) * 1973-05-17 1977-03-29 Ciba-Geigy Ag Preparation for the processing of photographic materials
US4111697A (en) * 1976-03-29 1978-09-05 Agfa-Gevaert, N. V. Novel antifogging and/or stabilizing compounds for silver halide photography

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US3368898A (en) * 1963-10-17 1968-02-13 Gen Aniline & Film Corp Autopositive film and paper and emulsions therefor
DE1281842B (de) * 1964-06-22 1968-10-31 Du Pont Fotografisches Aufzeichnungsmaterial mit einer fotoloeslichen Schicht
US3341574A (en) * 1964-09-18 1967-09-12 Celanese Corp Di-(neopentylglycol mononeoheptanoate)azelate
US3407067A (en) * 1964-10-13 1968-10-22 Du Pont Photosolubilization with mercaptooxazoles
US3407068A (en) * 1964-10-13 1968-10-22 Du Pont Photosolubilization
US3394005A (en) * 1964-10-16 1968-07-23 Du Pont Increased development rate of photosoluble silver halide emulsions by the action of water-soluble iodide
US3377169A (en) * 1965-03-30 1968-04-09 Du Pont Copper thallium and lead halide and pseudohalides photosoluble crystals
US3458318A (en) * 1965-08-02 1969-07-29 Eastman Kodak Co Supersensitized silver halide emulsions
US3451819A (en) * 1965-08-09 1969-06-24 Du Pont Photosoluble silver halide emulsion made spontaneously developable with amine boranes
US3464822A (en) * 1965-09-13 1969-09-02 Du Pont Process for making electrically conductive images
GB1178800A (en) * 1966-03-01 1970-01-21 Minnesota Mining & Mfg Improvements in or relating to Copying Materials
US3495982A (en) * 1967-06-23 1970-02-17 Du Pont Process for dissolution development using thiourea compounds as dmax maintainers
US3628956A (en) * 1967-12-08 1971-12-21 Du Pont Process for preparing direct positive images by photosolubilization
US3862352A (en) * 1968-04-16 1975-01-21 Itek Corp Photographically prepared electrical circuits wherein the photosensitive material is a photoconductor
US3649289A (en) * 1968-10-21 1972-03-14 Eastman Kodak Co Photographic materials
US3653899A (en) * 1968-11-12 1972-04-04 Eastman Kodak Co Photographic materials and processes
US3640717A (en) * 1969-06-05 1972-02-08 Itek Corp Photographic reversal process employing organic mercaptan compounds
US3652279A (en) * 1969-07-18 1972-03-28 Du Pont Nitrogen-containing dmax maintainers for use in photosoluble emulsions
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US3647439A (en) * 1968-10-01 1972-03-07 Eastman Kodak Co Photographic element, composition and process
US4014699A (en) * 1973-05-17 1977-03-29 Ciba-Geigy Ag Preparation for the processing of photographic materials
US4111697A (en) * 1976-03-29 1978-09-05 Agfa-Gevaert, N. V. Novel antifogging and/or stabilizing compounds for silver halide photography

Also Published As

Publication number Publication date
US3155507A (en) 1964-11-03
US3155515A (en) 1964-11-03
FR89467E (enrdf_load_stackoverflow)
GB1124772A (en) 1968-08-21
DE1261397B (de) 1968-02-15
DE1226877B (de) 1966-10-13
GB1031902A (en) 1966-06-02
BE670823A (enrdf_load_stackoverflow) 1966-04-12
US3155519A (en) 1964-11-03
DE1294186B (de) 1969-09-11
US3418124A (en) 1968-12-24
DE1293582B (de) 1969-04-24
US3155514A (en) 1964-11-03
US3384485A (en) 1968-05-21
DE1293581B (de) 1969-04-24
GB1031903A (en) 1966-06-02
GB1111226A (en) 1968-04-24
US3284206A (en) 1966-11-08

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