US3656955A - Silver halide emulsion sensitized with pentathiepane - Google Patents

Silver halide emulsion sensitized with pentathiepane Download PDF

Info

Publication number
US3656955A
US3656955A US68041A US3656955DA US3656955A US 3656955 A US3656955 A US 3656955A US 68041 A US68041 A US 68041A US 3656955D A US3656955D A US 3656955DA US 3656955 A US3656955 A US 3656955A
Authority
US
United States
Prior art keywords
group
compound
photographic emulsion
emulsion
silver halide
Prior art date
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
Application number
US68041A
Inventor
Yoshuke Ushimaru
Yosuke Nakajima
Mitsunori Sugiyama
Fumihiko Nishio
Shigeru Kobayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3656955A publication Critical patent/US3656955A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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

  • ABSTRACT A photosensitive silver halide photographic emulsion containing at least one compound selected from the group consisting of compounds having the formula 9 Claims, No Drawings SILVER HALIDE EMULSION SENSITIZED WITH PENTATI-IIEPANE BACKGROUND OF THE INVENTION 1 Field of the Invention
  • the present invention relates to a silver halide photographic emulsion. More particularly, the present invention relates to a silver halide photographic emulsion which is chemically sensitized with a sulfur-containing compound.
  • An object of the present invention is to increase the sensitivity of photosensitive silver halide photographic emulsions.
  • a chemically sensitizing process For example, compounds containing a labile sulfur (for example, sodium thiosulfate or thio-urea derivatives) are known as sulfur sensitizing agents. Also, a reducing agent, such as stannous chloride and hydrazine, is known as a reducing sensitizing agent. Some of these labile sulfur-containing compounds and reducing substances are considered to be contained in a natural gelatin for photography. Certain aurous or auric salts, for example aurous thiocyanate, have a chemically sensitizing action, and the method of utilizing this action is well known.
  • a labile sulfur for example, sodium thiosulfate or thio-urea derivatives
  • a reducing agent such as stannous chloride and hydrazine
  • the present inventors have found that a compound represented by the general formula DETAILED DESCRIPTION OF THE INVENTION
  • the above compound is a useful sensitizing agent regardless of whether the emulsion is a silver chloride emulsion, a silver bromide emulsion, a silver iodide emulsion, or a mixed silver halide emulsion, or, further, whether the emulsion is a waterwashed or a water-unwashed emulsion.
  • Suitable chemical sensitizers having the above formula are However, the chemical sensitizers used in the present invention are not limited to these compounds.
  • the optimum amount of the sulfur sensitizer having the above described formula to be used is dependent on the specific compound selected, the type of silver halide, the particle size ripening temperature, the ripening time, and the pH and the pAg of the silver halide emulsion. However, the amount generally used is in the range of from 0.01 to mg per 1 mole of silver halide. However, where the sensitizer is used in combination with other sensitizers, the amount used can be smaller; Where the sensitizer is used in combination with any appropriate antifoggant, the amount can be larger.
  • the sulfur sensitizer used in the present invention can be used in combination with reducing sensitizers such as stannous chloride or thiourea dioxide, and also can be combined with auric or aurous salts, such as aurous thiocyanate, platinum salts, palladium salts, or sulfuncontaining compounds such as sodium thiosulfate, thiourea derivatives, and further can be used together with polyoxyalkylene compounds having a molecular weight of above 300 or onium compounds.
  • reducing sensitizers such as stannous chloride or thiourea dioxide
  • auric or aurous salts such as aurous thiocyanate, platinum salts, palladium salts, or sulfuncontaining compounds such as sodium thiosulfate, thiourea derivatives
  • the sulfur-containing compound represented by the above described formula according to the present invention can be used not only in case of spectral sensitization but also without such sensitization. These can be usually applied to emulsions for black and white photography, for color photography, for X-ray, and for graphics.
  • the sulfur-containing compound represented by the above formula can be added to the photographic emulsion without any deleterious effects on stabilizers, antifoggants, hardeners, color developing agents, coating agents, and other emulsion additives.
  • the sulfur sensitizing agent represented by the above described formula is extremely useful for sensitizing a silver halide emulsion made of an inert gelatin and also can be used for sensitizing a silver halide emulsion in which at least one part of the protective colloid comprises other hydrophillic colloids such as a photographically labile gelatin or a polyvinylalcoho].
  • the sulfur sensitizing agent is particularly valuable in that the sensitizing efi'ect is markedly increased in combination with a thiosulfate ion, Le. a compound giving rise to a thiosulfate ion.
  • EXAMPLE 1 A highly sensitive neutral gelatino-silver bromo-iodide emulsion (5.0 percent silver iodide and 95.0 percent silver bromide) at the beginning of the chemical ripening was divided into five equal parts (Samples A to E). Samples C to E were mixed with Compound 1 in an alcohol solution and Sample B was mixed with a sensitizing natural gelatin, and were added with, as a metallic sensitizing agent, 7.5 mg of potassium chloroaurate (tetrahydrate) and 150 mg of potassium thiocyanate per 1 mole of silver halide in the form of an aqueous solution, and were chemically ripened under stirring at 50 C for 60 minutes.
  • Samples C to E were mixed with Compound 1 in an alcohol solution and Sample B was mixed with a sensitizing natural gelatin, and were added with, as a metallic sensitizing agent, 7.5 mg of potassium chloroaurate (tetrahydrate) and 150 mg of potassium thiocyanate per 1 mole of silver
  • EXAMPLE 2 A neutral gelatino-silver bromochloride emulsion (58.0 mole percent silver bromide and 42.0 mole percent silver chloride) for a fine grained positive film at the beginning of chemical ripening was divided into three equal parts (Samples I F to H). Compound 2 in a methyl alcohol solution was added to Sample H and a sensitive natural gelatin was added to Sample G in the amount as shown in Table 2.
  • a highly sensitive neutral gelatino-silver bromoiodide emulsion for an outer type reverse color film at the beginning of chemical ripening was divided into five equal parts (Samples I to M) and Compound 2 in a methyl alcohol solution was 7 added to each of samples K to M, and a sensitizing natural gelatin was added to Sample J in the amount as shown in Table 3.
  • Samples I to M Compound 2 in a methyl alcohol solution was 7 added to each of samples K to M, and a sensitizing natural gelatin was added to Sample J in the amount as shown in Table 3.
  • To each of these five types of emulsions were added 7.5 mg of potassium chloroaurate tetrahydrate and 150 mg of potassium thiocyanate per 1 mole of silver halide in the form of an aqueous solution and was chemically ripened at 50 C under stirring for 70 minutes.
  • N-Methyl-para-aminophcnol Sulfate 1.0 g Sodium Sulfite (anhydrous) 60.0 g Hydroquinone 10.0 g Potassium Bromide 5.0 g Potassium Thiocyanate 1.5 g Potassium lodide (0.1%) 5.0 ml Sodium Hydroxide 2.0 g Water to 1000 ml TABLE 3 Added Sulfur amount, Relative Sample sensitizer mole/AgX sensitivity Gamma For:
  • EXAMPLE 4 A semi-ammonium process gelatino-silver bromoiodide emulsion (1.5 mole percent silver iodide and 98.5 mole percent silver bromide) at the beginning of chemical ripening was divided into three equal parts (Samples N to P) and to Sample 0 to P were respectively added compounds 1 and 2 in a methylalcohol solution in the amount shown in Table 4. Next, to Sample N were added 4.7 mg of sodium thiosulfate (pentahydrate) and 1.2 mg of sodium aurous thiosulfate (dihydrate) Na Au(S O .2l-l O in the form of an aqueous solution per 1 mole of silver halide.
  • Sample O was added with 4.7 mg and 3.2 X10- mg of these salts per 1 mole of silver halide, respectively.
  • Sample P was added with only 1.2 mg of sodium aurous thiosulfate (dihydrate) per 1 mole of silver halide.
  • each of R R R and R is selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group; and wherein R and R or R and R, can combine to form a cycloalkyl group.
  • each of R R R R and R is selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group and a phenethyl group; and wherein R, and R or R and R, can combine to form a member selected from the group consisting of a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
  • thiosulfate compound is selected from the group consisting of sodium thiosulfate, sodium aurous thiosulfate and mixtures thereof.
  • a photosensitive element comprising a support having thereon at least a layer of the silver halide photographic emulsion as claimed in claim 1.

Abstract

A photosensitive silver halide photographic emulsion containing at least one compound selected from the group consisting of compounds having the formula

WHEREIN EACH OF R1, R2, and R3 and R4 is selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group; and wherein R1 and R2, or R3 and R4 can combine to form a cycloalkyl group, is disclosed.

Description

United States Patent Ushimaru et al.
[15] 3,656,955 [451 Apr. 18, W72
SILVER HALIDE EMULSION SENSITIZED WITH PENTATHIEPANE Inventors: Yoshuke Ushimaru; Yosuke Nakajima; Mitsunori Sugiyama; Fumihiko Nishio, Kanagawa; Shigeru Kobayashi, Osaka, all
of Japan Assignee: Fuji Photo Film Co., Ltd., Kanagawa,
Japan Filed: Aug. 28, 1970 Appl. No.: 68,041
Foreign Application Priority Data Aug. 28, 1969 Japan ..44/68219 US. Cl. ..96/107, 260/327 R Int. Cl
Field of Search ..96/ 107; 260/327 R [56] References Cited UNITED STATES PATENTS 3,503,758 3/ 1970 Wada et a1. ..260/327 R Primary Examiner-Norman G, Torchin Assistant Examiner-Won H. Louie, Jr. Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A photosensitive silver halide photographic emulsion containing at least one compound selected from the group consisting of compounds having the formula 9 Claims, No Drawings SILVER HALIDE EMULSION SENSITIZED WITH PENTATI-IIEPANE BACKGROUND OF THE INVENTION 1 Field of the Invention The present invention relates to a silver halide photographic emulsion. More particularly, the present invention relates to a silver halide photographic emulsion which is chemically sensitized with a sulfur-containing compound.
2. Description of the Prior Art An object of the present invention is to increase the sensitivity of photosensitive silver halide photographic emulsions.
Various methods for increasing the sensitivity of photosensitive silver halide photographic emulsions during manufacture are known as a chemically sensitizing process. For example, compounds containing a labile sulfur (for example, sodium thiosulfate or thio-urea derivatives) are known as sulfur sensitizing agents. Also, a reducing agent, such as stannous chloride and hydrazine, is known as a reducing sensitizing agent. Some of these labile sulfur-containing compounds and reducing substances are considered to be contained in a natural gelatin for photography. Certain aurous or auric salts, for example aurous thiocyanate, have a chemically sensitizing action, and the method of utilizing this action is well known.
SUMMARY OF THE INVENTION The present inventors have found that a compound represented by the general formula DETAILED DESCRIPTION OF THE INVENTION The above compound is a useful sensitizing agent regardless of whether the emulsion is a silver chloride emulsion, a silver bromide emulsion, a silver iodide emulsion, or a mixed silver halide emulsion, or, further, whether the emulsion is a waterwashed or a water-unwashed emulsion.
Suitable chemical sensitizers having the above formula are However, the chemical sensitizers used in the present invention are not limited to these compounds.
The optimum amount of the sulfur sensitizer having the above described formula to be used is dependent on the specific compound selected, the type of silver halide, the particle size ripening temperature, the ripening time, and the pH and the pAg of the silver halide emulsion. However, the amount generally used is in the range of from 0.01 to mg per 1 mole of silver halide. However, where the sensitizer is used in combination with other sensitizers, the amount used can be smaller; Where the sensitizer is used in combination with any appropriate antifoggant, the amount can be larger.
The sulfur sensitizer used in the present invention can be used in combination with reducing sensitizers such as stannous chloride or thiourea dioxide, and also can be combined with auric or aurous salts, such as aurous thiocyanate, platinum salts, palladium salts, or sulfuncontaining compounds such as sodium thiosulfate, thiourea derivatives, and further can be used together with polyoxyalkylene compounds having a molecular weight of above 300 or onium compounds.
The sulfur-containing compound represented by the above described formula according to the present invention can be used not only in case of spectral sensitization but also without such sensitization. These can be usually applied to emulsions for black and white photography, for color photography, for X-ray, and for graphics.
The sulfur-containing compound represented by the above formula can be added to the photographic emulsion without any deleterious effects on stabilizers, antifoggants, hardeners, color developing agents, coating agents, and other emulsion additives.
The sulfur sensitizing agent represented by the above described formula is extremely useful for sensitizing a silver halide emulsion made of an inert gelatin and also can be used for sensitizing a silver halide emulsion in which at least one part of the protective colloid comprises other hydrophillic colloids such as a photographically labile gelatin or a polyvinylalcoho].
The sulfur sensitizing agent is particularly valuable in that the sensitizing efi'ect is markedly increased in combination with a thiosulfate ion, Le. a compound giving rise to a thiosulfate ion.
The synthesis of the compounds represented by the above formula is described in Tetrahedron Letters No. 6,576 (1966) for Compounds 1, Acta Chemica Scandinavia 13 1032 and 1715 1959) for Compound 2 and 4, respectively, and Fredge. A.Acta Chem. Scand. 12 891 (1958) for Compound 3.
The present invention is illustrated fiirther by reference to the following examples.
EXAMPLE 1 A highly sensitive neutral gelatino-silver bromo-iodide emulsion (5.0 percent silver iodide and 95.0 percent silver bromide) at the beginning of the chemical ripening was divided into five equal parts (Samples A to E). Samples C to E were mixed with Compound 1 in an alcohol solution and Sample B was mixed with a sensitizing natural gelatin, and were added with, as a metallic sensitizing agent, 7.5 mg of potassium chloroaurate (tetrahydrate) and 150 mg of potassium thiocyanate per 1 mole of silver halide in the form of an aqueous solution, and were chemically ripened under stirring at 50 C for 60 minutes. Further to 1 kg of each emulsion were added 30 mg of 3,3-diethyl-9-methylthiocarbocyamine bromide, 450 mg of chrome alum and mg of saponine and the mixture was coated on a cellulose triacetate base film and dried to obtain a photosensitive material of 14 microns in coating thickness. Next, the material so obtained was exposed stepwise to a light source of 5,400 1C for 1/50 second, developed with a developer having the following composition at 20 C for 10 minutes, fixed, washed with water, and, after drying, sensitometry was carried out. The results obtained are shown in Table 1.
Developer Composition N-Mehtyl-para-aminophenol Sulfate 2.0 g Sodium Sulfite (anhydrous) 100.0 g Hydroquinone 5.0 g Borax 2.0 g Water to 1000 ml TABLE 1 Added Sulfur amount, Relative Sample sensitizer mole/AgX sensitivity Gamma Fog A 100 0. 52 0. 04 B sensitizing 10.0 g 1,120 1.02 0.12
natural gelatin.
C Compound 1. 55 mg 1,100 1.04 0.07 D. Compound 2 60 mg 1, 240 1. 07 0. Compound 3. 65 mg 1.01 0.10
As can be seen from Table 1, a marked sensitizing effect was observed.
EXAMPLE 2 A neutral gelatino-silver bromochloride emulsion (58.0 mole percent silver bromide and 42.0 mole percent silver chloride) for a fine grained positive film at the beginning of chemical ripening was divided into three equal parts (Samples I F to H). Compound 2 in a methyl alcohol solution was added to Sample H and a sensitive natural gelatin was added to Sample G in the amount as shown in Table 2. Next, after ripening at 52 C for 3 minutes to 1 kg of each emulsion were added 300 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 450 mg of chrome alum, and 120 mg of soponine, and the mixture was coated on a cellulose triacetate film base and dried to obtain a photosensitive material of 12 microns in coating thickness. The material so obtained was exposed stepwise to a light source of 2,660 K for l/20 second, developed with a developer having the following composition, fixed, washed with water and, after drying, sensitometry was conducted. The results obtained are shown in Table 2.
Developer Composition N-Methyl-para-aminophenol Sulfate 1.4 g lsomeric Potassium Bisulfite 8.0 g Hydroquinone 6.0 g Sodium Carbonate (mono hydrate) 22.5 g Citric Acid 0.7 g Potassium Bromide 0.9 g Water to 1000 ml As can be seen from the results in Table 2, a marked sensitizing effect was obtained.
A highly sensitive neutral gelatino-silver bromoiodide emulsion for an outer type reverse color film at the beginning of chemical ripening was divided into five equal parts (Samples I to M) and Compound 2 in a methyl alcohol solution was 7 added to each of samples K to M, and a sensitizing natural gelatin was added to Sample J in the amount as shown in Table 3. Next, to each of these five types of emulsions were added 7.5 mg of potassium chloroaurate tetrahydrate and 150 mg of potassium thiocyanate per 1 mole of silver halide in the form of an aqueous solution and was chemically ripened at 50 C under stirring for 70 minutes. Further, to 1 kg of the emulsion were added 30 g of 1,3-diethyl-5'-methoxy-6-methyl-seleno- Z-cyanineiodide, 450 mg of chrome alum and 120 mg of saponine, and the mixture was coated on a cellulose triacetate film base and dried to obtain a sensitive material of 8 micron in coating thickness. Next, the material so obtained was exposed stepwise to a light source of 5,400 K for l/20 second, developed using a developer having the following composition at 27 C for 3%minutes, fixed, washed with water and, after drying, sensitometry was carried out. The results obtained are shown in Table 3.
Developer Composition N-Methyl-para-aminophcnol Sulfate 1.0 g Sodium Sulfite (anhydrous) 60.0 g Hydroquinone 10.0 g Potassium Bromide 5.0 g Potassium Thiocyanate 1.5 g Potassium lodide (0.1%) 5.0 ml Sodium Hydroxide 2.0 g Water to 1000 ml TABLE 3 Added Sulfur amount, Relative Sample sensitizer mole/AgX sensitivity Gamma For:
I A 100 0. 49 O. 0!] J sensitizing 080 0. 84 0. 10
natural gelatin.
K Compound 2. 1,020 0. 87 0.10 L. 1,150 0.07 0.13 0. 0. 15
As can be seen from the results shown in Table 3, a marked sensitizing efiect was obtained.
EXAMPLE 4 A semi-ammonium process gelatino-silver bromoiodide emulsion (1.5 mole percent silver iodide and 98.5 mole percent silver bromide) at the beginning of chemical ripening was divided into three equal parts (Samples N to P) and to Sample 0 to P were respectively added compounds 1 and 2 in a methylalcohol solution in the amount shown in Table 4. Next, to Sample N were added 4.7 mg of sodium thiosulfate (pentahydrate) and 1.2 mg of sodium aurous thiosulfate (dihydrate) Na Au(S O .2l-l O in the form of an aqueous solution per 1 mole of silver halide. In the same manner, Sample O was added with 4.7 mg and 3.2 X10- mg of these salts per 1 mole of silver halide, respectively. Sample P was added with only 1.2 mg of sodium aurous thiosulfate (dihydrate) per 1 mole of silver halide.
Thereafter, these emulsions were chemically ripened at 50 C for 70 minutes.
These three types of emulsions were coated on a polyethylene terephthalate film base and dried to obtain a photosensitive material of 8 microns in coating thickness. Next, the materials so obtained were exposed through a continuous wedge to a light source of 5,400 K, and developed using a developer having the following composition at 20 C for 4 minutes.
Developer Composition N-Mehtyl-para-aminophenol Sulfate 4.0 g Sodium Sulfite (anhydrous) 60.0 g Hydroquinone 10.0 g Sodium carbonate (monohydrate) 53.0 g Sodium Bromide 3.0 g Water to 1000 ml After the samples were fixed, washed with water and dried, sensitometry was conducted to obtain the results shown in Table 4.
TABLE 4 Added Relaamount, tive Sulfur sensitizing mole/AgX sensi- Sample agent (mg) tivity Gamma Fog Na2S2O3-5H2O 4. 7. N. {l\Ia3Au(SQ03)2 2 1.2 100 1. 75 0.15
NazS2Oa-5H2O 4. 7 O h Na3Au(Sz03)2'H2O. 3 2X102 118 l. 85 0. 14
compousng 1) 1. 2 NaaA11( 2 3 221120." 1.2 P 2 u an 110 1. 35 0.15
in s s R4 wherein each of R R R and R is selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group; and wherein R and R or R and R, can combine to form a cycloalkyl group.
2. The photographic emulsion as claimed in claim 1, wherein each of R R R and R is selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group and a phenethyl group; and wherein R, and R or R and R, can combine to form a member selected from the group consisting of a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
3. The photographic emulsion as claimed in claim 1, wherein said compound is e mo CH2 s s s 4. The photographic emulsion as claimed in claim 1, wherein said compound is 5. The photographic emulsion as claimed in claim 1 wherein said compound is CHzOH CHz ss omomorn 011201120112 s s CHzCHzCH 6. The photographic emulsion as claimed in claim 1, wherein said compound is 7. The photographic emulsion as claimed in claim 1, wherein said emulsion contains additionally at least one compound having a thiosulfate ion.
8. The photographic emulsion as claimed in claim 7, wherein the thiosulfate compound is selected from the group consisting of sodium thiosulfate, sodium aurous thiosulfate and mixtures thereof.
9. A photosensitive element comprising a support having thereon at least a layer of the silver halide photographic emulsion as claimed in claim 1.

Claims (8)

  1. 2. The photographic emulsion as claimed in claim 1, wherein each of R1, R2, R3 and R4 is selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group and a phenethyl group; and wherein R1 and R2 or R3 and R4 can combine to form a member selected from the group consisting of a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
  2. 3. The photographic emulsion as claimed in claim 1, wherein said compound is
  3. 4. The photographic emulsion as claimed in claim 1, wherein said compound is
  4. 5. The photographic emulsion as claimed in claim 1, wherein said compound is
  5. 6. The photographic emulsion as claimed in claim 1, wherein said compound is
  6. 7. The photographic emulsion as claimed in claim 1, wherein said emulsion contains additionally at least one compound having a thiosulfate ion.
  7. 8. The photographic emulsion as claimed in claim 7, wherein the thiosulfate compound is selected from the group consisting of sodium thiosulfate, sodium aurous thiosulfate and mixtures thereof.
  8. 9. A photosensitive element comprising a support having thereon at least a layer of the silver halide photographic emulsion as claimed in claim 1.
US68041A 1969-08-28 1970-08-28 Silver halide emulsion sensitized with pentathiepane Expired - Lifetime US3656955A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44068219A JPS4912421B1 (en) 1969-08-28 1969-08-28

Publications (1)

Publication Number Publication Date
US3656955A true US3656955A (en) 1972-04-18

Family

ID=13367456

Family Applications (1)

Application Number Title Priority Date Filing Date
US68041A Expired - Lifetime US3656955A (en) 1969-08-28 1970-08-28 Silver halide emulsion sensitized with pentathiepane

Country Status (7)

Country Link
US (1) US3656955A (en)
JP (1) JPS4912421B1 (en)
BE (1) BE755357A (en)
CA (1) CA942986A (en)
DE (1) DE2042359C3 (en)
FR (1) FR2059245A5 (en)
GB (1) GB1319548A (en)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857711A (en) * 1970-12-21 1974-12-31 Fuji Photo Film Co Ltd Silver halide photographic emulsion sensitized with a heterocyclic compound containing 4-sulfur atoms
US4054457A (en) * 1976-12-17 1977-10-18 E. I. Du Pont De Nemours And Co. Silver halide emulsions containing hexathiocane thiones as sensitizers
US4210716A (en) * 1979-01-31 1980-07-01 E. I. Du Pont De Nemours And Company Silver halide emulsion containing tetrathiocino diisothiazoles as antifoggers
EP0106306A2 (en) 1982-10-14 1984-04-25 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0115351A2 (en) 1983-01-28 1984-08-08 Fuji Photo Film Co., Ltd. Silver halide light-sensitive material
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0200206A2 (en) 1985-04-30 1986-11-05 Konica Corporation Silver halide photographic light-sensitive material
EP0201027A2 (en) 1985-04-30 1986-11-12 Konica Corporation Silver halide photographic light-sensitive material
EP0202784A2 (en) 1985-04-23 1986-11-26 Konica Corporation Silver halide photographic light-sensitive material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0239363A2 (en) 1986-03-25 1987-09-30 Konica Corporation Light-sensitive silver halide photographic material feasible for high speed processing
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
EP0514675A1 (en) 1991-04-22 1992-11-25 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for processing the same
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0580041A2 (en) 1992-07-10 1994-01-26 Fuji Photo Film Co., Ltd. Method of processing silver halide photographic material and composition for processing
EP0589460A1 (en) 1992-09-24 1994-03-30 Fuji Photo Film Co., Ltd. Method for processing a black & white silver halide light-sensitive material
US5318887A (en) * 1991-06-06 1994-06-07 Konica Corporation Method for production of silver halide emulsion, and silver halide photographic light-sensitive material
US5389511A (en) * 1991-11-06 1995-02-14 Konica Corporation Silver halide photographic emulsion and light-sensitive silver halide photographic material making use of the same
EP0693710A1 (en) 1994-07-18 1996-01-24 Konica Corporation Silver halide photographic element and processing method thereof
US5800975A (en) * 1994-12-14 1998-09-01 Konica Corporation Silver halide photographic light sensitive material
EP0809138B1 (en) * 1996-05-23 2001-08-29 Eastman Kodak Company Xanthate salts as chemical sensitizers for silver halides
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9512899D0 (en) * 1995-06-23 1995-08-23 Minnesota Mining & Mfg Alteration of image tone in black and white photographic materials

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3503758A (en) * 1965-10-14 1970-03-31 Takeda Chemical Industries Ltd Flavoring composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3503758A (en) * 1965-10-14 1970-03-31 Takeda Chemical Industries Ltd Flavoring composition

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857711A (en) * 1970-12-21 1974-12-31 Fuji Photo Film Co Ltd Silver halide photographic emulsion sensitized with a heterocyclic compound containing 4-sulfur atoms
US4054457A (en) * 1976-12-17 1977-10-18 E. I. Du Pont De Nemours And Co. Silver halide emulsions containing hexathiocane thiones as sensitizers
US4210716A (en) * 1979-01-31 1980-07-01 E. I. Du Pont De Nemours And Company Silver halide emulsion containing tetrathiocino diisothiazoles as antifoggers
EP0106306A2 (en) 1982-10-14 1984-04-25 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0115351A2 (en) 1983-01-28 1984-08-08 Fuji Photo Film Co., Ltd. Silver halide light-sensitive material
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0202784A2 (en) 1985-04-23 1986-11-26 Konica Corporation Silver halide photographic light-sensitive material
EP0200206A2 (en) 1985-04-30 1986-11-05 Konica Corporation Silver halide photographic light-sensitive material
EP0201027A2 (en) 1985-04-30 1986-11-12 Konica Corporation Silver halide photographic light-sensitive material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0239363A2 (en) 1986-03-25 1987-09-30 Konica Corporation Light-sensitive silver halide photographic material feasible for high speed processing
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
EP0514675A1 (en) 1991-04-22 1992-11-25 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for processing the same
US5318887A (en) * 1991-06-06 1994-06-07 Konica Corporation Method for production of silver halide emulsion, and silver halide photographic light-sensitive material
US5389511A (en) * 1991-11-06 1995-02-14 Konica Corporation Silver halide photographic emulsion and light-sensitive silver halide photographic material making use of the same
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0580041A2 (en) 1992-07-10 1994-01-26 Fuji Photo Film Co., Ltd. Method of processing silver halide photographic material and composition for processing
EP0589460A1 (en) 1992-09-24 1994-03-30 Fuji Photo Film Co., Ltd. Method for processing a black & white silver halide light-sensitive material
EP0693710A1 (en) 1994-07-18 1996-01-24 Konica Corporation Silver halide photographic element and processing method thereof
US5556738A (en) * 1994-07-18 1996-09-17 Konica Corporation Silver halide photographic element and processing method thereof
US5800975A (en) * 1994-12-14 1998-09-01 Konica Corporation Silver halide photographic light sensitive material
EP0809138B1 (en) * 1996-05-23 2001-08-29 Eastman Kodak Company Xanthate salts as chemical sensitizers for silver halides
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
US7220537B2 (en) 2003-01-31 2007-05-22 Konica Minolta Photo Imaging, Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

Also Published As

Publication number Publication date
DE2042359A1 (en) 1971-03-18
GB1319548A (en) 1973-06-06
FR2059245A5 (en) 1971-05-28
BE755357A (en) 1971-02-01
DE2042359C3 (en) 1979-09-06
CA942986A (en) 1974-03-05
JPS4912421B1 (en) 1974-03-25
DE2042359B2 (en) 1979-01-11

Similar Documents

Publication Publication Date Title
US3656955A (en) Silver halide emulsion sensitized with pentathiepane
US2566245A (en) Complex compounds of the platinum group as photographic fog inhibitors
US3220839A (en) Photographic emulsions containing isothiourea derivatives
US2598079A (en) High-speed photographic silver halide emulsions supersensitized with palladium salts
US2983609A (en) Chemical sensitization of photographic emulsions
US3071465A (en) Fog reduction in silver halide emulsions by 2h-tetrazolium halides
US3519426A (en) Preparation of silver halide emulsions having high covering power
US3544336A (en) Phosphate antifoggants for photographic emulsions
US4067740A (en) Trithiocarbonates as sensitizers for silver halide emulsions
US2728664A (en) Photographic emulsions containing mercury salts
US3060028A (en) Stabilized photographic silver halide emulsions containing iodine complexes of poly-n-vinyl-2-oxazolidinones
US3857711A (en) Silver halide photographic emulsion sensitized with a heterocyclic compound containing 4-sulfur atoms
US4423140A (en) Silver halide emulsions containing aromatic latent image stabilizing compounds
US3597213A (en) Fog reduction in photographic silver halide emulsions
US3607278A (en) Photographic elements containing fogged and unfogged silver halide grains and a slow silver halide emulsion layer
US3930860A (en) Spectrally sensitized color photographic materials suitable for high temperature rapid development
US3554758A (en) Photographic light-sensitive material
US3622329A (en) Photographic silver halide emulsions with increased sensitivity
US3689273A (en) Silver halide emulsion containing sulfur or selenium sensitizer and hydroxy tetra-azaindene stabilizer
US3006762A (en) Sensitizers for photographic emulsions
US3615490A (en) Photographic overcoat comprising a benzotriazole toning agent and a silver salt of 5-mercapto-1-substituted tetrazole
US3619198A (en) Silver halide emulsions containing hydroxy substituted alicyclic compounds
US3591385A (en) Silver halide emulsions sensitized with a combination of sulfur and selenium for color photography
US3062645A (en) Sensitization of photographic emulsions to be developed with p-phenylenediamine developing agents
US3173790A (en) Silver halide emusions containing polyoxyalkylene sensitizers