US3501313A - Photographic silver halide emulsions which include high efficiency sulfurcontaining sensitizers - Google Patents
Photographic silver halide emulsions which include high efficiency sulfurcontaining sensitizers Download PDFInfo
- Publication number
- US3501313A US3501313A US585732A US3501313DA US3501313A US 3501313 A US3501313 A US 3501313A US 585732 A US585732 A US 585732A US 3501313D A US3501313D A US 3501313DA US 3501313 A US3501313 A US 3501313A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- emulsion
- emulsions
- sensitizers
- silver
- 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
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
Definitions
- Photographic light-sensitive emulsions which include a sensitizer having the formula wherein:
- A is a sulphur atom
- each of R R R and R is hydrogen, alkyl, or aryl, or
- R and R and/ or R and R together are the atoms necessary to close a heterocyclic ring
- n zero or one.
- the present invention relates to chemically sensitized, photographic, light-sensitive silver halide emulsions and to a photographic material comprising a light-sensitive layer coated from such emulsion.
- photographic silver halide emulsions can be chemically sensitized by means of dilierent kinds of compounds, which considerably enhance the sensitivity and sometimes the gradation too.
- the known chemical sensitizers can be divided into three main classes:
- A represents a single bond or a sulphur atom
- each of R R R and R represents a hydrogen atom, an alkyl radical including a substituted alkyl radical, an aralkyl radical, and a substituted aralkyl radical, or an aryl radical including a substituted aryl radical or R and R and/ or R and R together represent the atoms necessary to close a heterocyclic ring including a substituted heterocyclic ring,
- the compounds according to the above general formula produce all kinds of other favourable side-efiects on the silver halide emulsion. For instance, they contribute in a considerable way to the homogeneity of the grain size in that they prevent the exceptional growth of some grains when present during the physical ripening of the silver halide emulsion.
- the compounds according to the general formula are very interesting when employed in the preparation of fine-grain silver halide emulsions, for instance emulsions the silver halide grains of which have an average diameter of less than 0.2 micron.
- the compounds according to the general formula are also particularly suitable as chemical sensitizers when used as a partial or full substitution for the usual sodium thiosulphate which, owing to the large specific grain surface of such fine-grain emulsions, would have to be added in large amounts. This would result in an undesirable growth of the silver halide grains since said large amount of thiosulphate would create a strong dissolving action.
- B is- (dimethyl-thioearb amoyl) sulphide H 8 CH N- C S C N H3 g g CH3 .1) Bis (pip eridino-thiocarb onyl) -sulphide CHr-CHZ CHz-CHZ HzC NC SCN CH2 cHrcfiz g g CH2Cfi2
- sulphur sensiizers according to the above general formula depend upon he compound chosen, the nature of the silver halide, he grain size, the desired rip
- the amounts used generally vary from bout 1 mg. to about 200 mg. per mole of silver halide. t is evident that smaller amounts of these compounds say be used too, e.g., when a little increase in sensitivity envisaged. When using larger amounts care should be zken that no fog arises.
- the new compounds may be used in combination with educing sensitizers such as tin (II) salts or thiourea di- -xide.
- educing sensitizers such as tin (II) salts or thiourea di- -xide.
- gold salts such as gold thiocyanate, platiurn salts and palladium salts.
- a considerable increase in ensitivity can also be obtained when applying the comounds according to the present invention in combination rith development accelerators such as polyoxyalkylene erivatives having a molecular weight higher than 500 nd onium compounds.
- the new sulphur sensitizers can be used in spectrally s well as in not spectrally sensitized emulsions. They are ucecssfully applied in common emulsions, in colour mulsions, in X-ray emulsions, in graphic emulsions, in .ippman emulsions and in fine grain emulsions for scienific purposes.
- the classical emulsion ingredients such as stabilizers, ntifogging agents, developing agents, hardening agents, olour couplers, softening agents, dispersing agents, etc., my be incorporated into the emulsion together with the ulphur sensitizers according to the invention without any etrimental interaction taking place.
- the use of the sulphur sensitizers according a the above general formula is of great technological nportance to sensitize silver halide emulsions prepared Ilth inert gelatin, it is also very interesting to use them or the sensitization of silver halide emulsions the proactive colloid of which at least partially consists of active elatin or other hydrophilic colloids such as polyvinyl lcohol.
- the compounds may also be used in ombination with known sulphur sensitizers in order to btain special effects such as very high maximum denities and high gradations together with high sensitivities.
- EXAMPLE 1 A silver bromo-iodide emulsion (3 mole percent of iodide) prepared with inert gelatin and having an average grain size of 0.5 micron, a pAg of 7.5 and a pH of 6.5 is divided into three equal parts (samples A, B and C). The sulphur sensitizers listed in Table I are added to samples B and C in the given concentrations. The emulsions are then ripened at 45 C. for 3 hours whereupon they are coated on a cellulose triacetate support.
- test-strips obtained are developed after exposure in a hydroquinone-p-rnonomethyl-aminophenol hemisulphate developer, fixed and rinsed whereupon the speed is meas ured.
- Table I the relative speeds are listed.
- a gold thiocyanate solution is added in an amount equivalent to 5 mg. of gold per mole of silver halide to a same emulsion as described in Example 1 just before dividing the emulsion in samples A, B and C and before the addition of compounds 2 and 3 in the given concentration to samples B and C.
- the three samples are coated and further treated as described in Example 1.
- the materials according to the present invention show a sensitivity that is 3 times as high as that of the light-sensitive material containing only gold rhodanide and no chemical sensitizer according to the present invention.
- EXAMPLE 3 An all-silver iodide emulsion prepared with inert gelatin and having a pAg of 9 and a pH of 6 .5 is divided into four equal parts A, B, C and D. To each part is added the chemical sensitizer listed in Table II hereinafter in the concentration given. After having been ripened for 1 hour at 50 C. the four emulsions are coated on a cellulose triacetate support. The light-sensitive materials obtained are exposed and further treated as described in Example 1. The relative speeds are given in Table II.
- EXAMPLE 4 TAB LE III Concentration per Sulphur sensitizer mole of silver halide Rel. speed 100 Sodium thiosulphate 0.7X10- mol 200 C Compound 10 0.7)(10- mole 350 EXAMPLE 5
- a gold thiocyanate solution is added, in an amount equivalent to 7 mg. of gold per mole of silver halide, before dividing the emulsion into samples, and adding a chemical sensitizer according to the invention.
- the emulsion is divided into two equal parts and to one part 0.7 mole of compound 10 per mole of silver chloride is added.
- the emulsions are coated and further treated as described in Example 4.
- the speed of the lightsensitive material comprising compound 10 is 3 times as high as that of the other material.
- EXAMPLE 6 An ammoniacal silver bromo iodide emulsion (3 mole percent of iodide) which has been prepared with inert gelatin, and which has not been washed as was the case with the emulsions of the preceding examples, is divided immediately after its preparation into 3 equal parts (samples A, B and C). The sulphur sensitizers listed in Table IV are added to samples B and C in the given concentrations. After having been kept for 30 min. at 35 C. the three samples are coated onto a cellulose triacetate support and further treated as in Example 1. The relative speeds of the three materials are listed in Table IV.
- 240 cc. of a 3M aqueous silver nitrate solution and 240 cc. of a 3M aqueous potassium bromide solution are simultaneously and slowly added at 35 C. to a solution of 50 g. of gelatin in 500 cc. of water (emulsion A).
- a second emulsion is prepared in the same way with the only difference that the aqueous gelatin solution to which the aqueous silver nitrate and the potassium bromide solutions are added also comprises 9 mg. of compound 2 (emulsion B).
- Emulsions A and -B are physically ripened by keeping them for 60 min. at 45 C.
- Electron micrographs (magnification 10.000 X) are taken from the ripened liquid emulsions. In both cases, these micrographs shows a dispersion of silver bromide grains ranging for the greater part from about 0.05 to about 0.11.0. Emulsion A, however, also contains a considerable number of grains ranging from about 0.5 to about 1.0 1. whereas emulsion B only contains some grains which are of larger size than 0.1,u. From the results obtained it clearly appears that the presence of a chemical sensitizer according to the present invention during the precipitation of the silver halide and the physical ripening of the emulsion obtained prevents in a very efiicient way the formation of large silver halide grains.
- Photographic light-sensitive silver halide emulsion containing as a sensitizer at least one compound corresponding to the following general formula:
- A is a sulphur atom
- each of R R R and R is hydrogen, alkyl, or aryl, or
- R and R and/or R and R together are the atoms necessary to close a heterocyclic ring
- n zero or one.
- Photographic light-sensitive emulsion according to claim 1 wherein the silver halide emulsion includes a protective colloid consisting substantially of inert gelatin.
- Photographic light-sensitive emulsion according to claim 1 wherein the emulsion is an unwashed silver halide emulsion.
- Photographic light-sensitive emulsion according to claim 1 wherein the silver halide of the emulsion consists substantially of silver chloride.
- Photographic light-sensitive emulsion according to claim 1 wherein the silver halide of the emulsion consists substantially of silver iodide.
- Photographic material comprising a light-sensitive silver halide emulsion layer applied from the silver halide emulsion of claim 1.
- Photographic light-sensitive emulsion according to claim 1 wherein the emulsion includes a polyoxyalkylene derivative having a molecular weight higher than 500.
- Photographic light-sensitive emulsion according to claim 1 wherein the emulsion includes an onium compound.
- Photographic light-sensitive emulsion according to claim 1 wherein the sensitizer is present in an amount of from 1 to 200 mg. per mole of silver halide.
- Photographic light-sensitive emulsion according to claim 1 wherein the emulsion includes a gold salt.
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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)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB42974/65A GB1099706A (en) | 1965-10-11 | 1965-10-11 | Silver halide emulsions and photographic materials comprising the same |
Publications (1)
Publication Number | Publication Date |
---|---|
US3501313A true US3501313A (en) | 1970-03-17 |
Family
ID=10426793
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US585732A Expired - Lifetime US3501313A (en) | 1965-10-11 | 1966-10-11 | Photographic silver halide emulsions which include high efficiency sulfurcontaining sensitizers |
Country Status (6)
Country | Link |
---|---|
US (1) | US3501313A (de) |
BE (1) | BE688064A (de) |
DE (1) | DE1522405A1 (de) |
FR (1) | FR1496597A (de) |
GB (1) | GB1099706A (de) |
NL (1) | NL6614292A (de) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3951665A (en) * | 1973-01-17 | 1976-04-20 | Ciba-Geigy Ag | Direct-positive silver halide emulsion fogged with a tin (II) chelate |
US4078937A (en) * | 1974-11-26 | 1978-03-14 | Fuji Photo Film Co., Ltd. | Process for sensitizing a fine grain silver halide photographic emulsion |
DE2755609A1 (de) * | 1976-12-17 | 1978-06-22 | Du Pont | Photographisches material |
DE2756353A1 (de) * | 1976-12-21 | 1978-06-22 | Du Pont | Photomaterial |
US4266018A (en) * | 1978-09-25 | 1981-05-05 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsions |
EP0112162A2 (de) | 1982-12-13 | 1984-06-27 | Konica Corporation | Lichtempfindliches photographisches Silberhalogenidmaterial |
EP0228084A2 (de) | 1985-12-25 | 1987-07-08 | Fuji Photo Film Co., Ltd. | Verfahren zur Herstellung eines Bildes |
US4786588A (en) * | 1985-09-20 | 1988-11-22 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
EP0514675A1 (de) | 1991-04-22 | 1992-11-25 | Fuji Photo Film Co., Ltd. | Photographische Silberhalogenidmaterialien und Verfahren zu ihren Verarbeitung |
EP0563708A1 (de) | 1992-03-19 | 1993-10-06 | Fuji Photo Film Co., Ltd. | Photographische Silberhalogenidemulsion und lichtempfindliches Material, das diese verwendet |
EP0580041A2 (de) | 1992-07-10 | 1994-01-26 | Fuji Photo Film Co., Ltd. | Verarbeitungszusammensetzung und Verfahren zur Verarbeitung eines photographischer Silberhalogenidmaterials |
EP0589460A1 (de) | 1992-09-24 | 1994-03-30 | Fuji Photo Film Co., Ltd. | Verarbeitungsverfahren für lichtempfindliches silberhalogenidenthaltendes Schwarzweissmaterial |
US5318887A (en) * | 1991-06-06 | 1994-06-07 | Konica Corporation | Method for production of silver halide emulsion, and silver halide photographic light-sensitive material |
US5342750A (en) * | 1992-04-24 | 1994-08-30 | Fuji Photo Film Co., Ltd. | Silver halide photographic material containing a tellurium compound |
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 (de) | 1994-07-18 | 1996-01-24 | Konica Corporation | Photographisches Silberhalogenidelement und sein Verarbeitungsverfahren |
EP0708370A2 (de) | 1994-10-18 | 1996-04-24 | Minnesota Mining And Manufacturing Company | Verfahren zur Herstellung Diffusionübertragungsdruckplatten |
EP0708371A2 (de) | 1994-10-18 | 1996-04-24 | Minnesota Mining And Manufacturing Company | Wirkungsfördernder Zusatz für Diffusionübertragungsdruckplatte |
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 |
WO2012035314A1 (en) | 2010-09-17 | 2012-03-22 | Fujifilm Manufacturing Europe Bv | Photographic paper |
WO2021213762A1 (en) | 2020-04-24 | 2021-10-28 | Fujifilm Manufacturing Europe Bv | Photographic paper |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3226232A (en) * | 1963-05-16 | 1965-12-28 | Gen Aniline & Film Corp | Fog reduction in silver halide emulsions with a diphenyldisulfide dicarboxylic acid |
US3287137A (en) * | 1962-09-11 | 1966-11-22 | Eastman Kodak Co | Light-developable silver halide emulsions |
-
1965
- 1965-10-11 GB GB42974/65A patent/GB1099706A/en not_active Expired
-
1966
- 1966-10-11 NL NL6614292A patent/NL6614292A/xx unknown
- 1966-10-11 BE BE688064D patent/BE688064A/xx unknown
- 1966-10-11 FR FR79932A patent/FR1496597A/fr not_active Expired
- 1966-10-11 DE DE19661522405 patent/DE1522405A1/de active Pending
- 1966-10-11 US US585732A patent/US3501313A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3287137A (en) * | 1962-09-11 | 1966-11-22 | Eastman Kodak Co | Light-developable silver halide emulsions |
US3226232A (en) * | 1963-05-16 | 1965-12-28 | Gen Aniline & Film Corp | Fog reduction in silver halide emulsions with a diphenyldisulfide dicarboxylic acid |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3951665A (en) * | 1973-01-17 | 1976-04-20 | Ciba-Geigy Ag | Direct-positive silver halide emulsion fogged with a tin (II) chelate |
US4078937A (en) * | 1974-11-26 | 1978-03-14 | Fuji Photo Film Co., Ltd. | Process for sensitizing a fine grain silver halide photographic emulsion |
DE2755609A1 (de) * | 1976-12-17 | 1978-06-22 | Du Pont | Photographisches material |
DE2756353A1 (de) * | 1976-12-21 | 1978-06-22 | Du Pont | Photomaterial |
US4266018A (en) * | 1978-09-25 | 1981-05-05 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsions |
EP0112162A2 (de) | 1982-12-13 | 1984-06-27 | Konica Corporation | Lichtempfindliches photographisches Silberhalogenidmaterial |
US4786588A (en) * | 1985-09-20 | 1988-11-22 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
EP0228084A2 (de) | 1985-12-25 | 1987-07-08 | Fuji Photo Film Co., Ltd. | Verfahren zur Herstellung eines Bildes |
EP0514675A1 (de) | 1991-04-22 | 1992-11-25 | Fuji Photo Film Co., Ltd. | Photographische Silberhalogenidmaterialien und Verfahren zu ihren Verarbeitung |
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 (de) | 1992-03-19 | 1993-10-06 | Fuji Photo Film Co., Ltd. | Photographische Silberhalogenidemulsion und lichtempfindliches Material, das diese verwendet |
US5342750A (en) * | 1992-04-24 | 1994-08-30 | Fuji Photo Film Co., Ltd. | Silver halide photographic material containing a tellurium compound |
EP0580041A2 (de) | 1992-07-10 | 1994-01-26 | Fuji Photo Film Co., Ltd. | Verarbeitungszusammensetzung und Verfahren zur Verarbeitung eines photographischer Silberhalogenidmaterials |
EP0589460A1 (de) | 1992-09-24 | 1994-03-30 | Fuji Photo Film Co., Ltd. | Verarbeitungsverfahren für lichtempfindliches silberhalogenidenthaltendes Schwarzweissmaterial |
EP0693710A1 (de) | 1994-07-18 | 1996-01-24 | Konica Corporation | Photographisches Silberhalogenidelement und sein Verarbeitungsverfahren |
US5556738A (en) * | 1994-07-18 | 1996-09-17 | Konica Corporation | Silver halide photographic element and processing method thereof |
EP0708370A2 (de) | 1994-10-18 | 1996-04-24 | Minnesota Mining And Manufacturing Company | Verfahren zur Herstellung Diffusionübertragungsdruckplatten |
EP0708371A2 (de) | 1994-10-18 | 1996-04-24 | Minnesota Mining And Manufacturing Company | Wirkungsfördernder Zusatz für Diffusionübertragungsdruckplatte |
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 |
WO2012035314A1 (en) | 2010-09-17 | 2012-03-22 | Fujifilm Manufacturing Europe Bv | Photographic paper |
WO2021213762A1 (en) | 2020-04-24 | 2021-10-28 | Fujifilm Manufacturing Europe Bv | Photographic paper |
Also Published As
Publication number | Publication date |
---|---|
FR1496597A (fr) | 1967-09-29 |
DE1522405A1 (de) | 1969-08-14 |
BE688064A (de) | 1967-04-11 |
GB1099706A (en) | 1968-01-17 |
NL6614292A (de) | 1967-03-28 |
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