US2739060A - Chemical sensitization of photographic emulsions - Google Patents
Chemical sensitization of photographic emulsions Download PDFInfo
- Publication number
- US2739060A US2739060A US319618A US31961852A US2739060A US 2739060 A US2739060 A US 2739060A US 319618 A US319618 A US 319618A US 31961852 A US31961852 A US 31961852A US 2739060 A US2739060 A US 2739060A
- Authority
- US
- United States
- Prior art keywords
- emulsion
- sensitizing
- sulfur
- emulsions
- gold
- 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
- 239000000839 emulsion Substances 0.000 title description 37
- 206010070834 Sensitisation Diseases 0.000 title description 3
- 230000008313 sensitization Effects 0.000 title description 3
- 239000000126 substance Substances 0.000 title description 3
- 230000001235 sensitizing effect Effects 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 21
- 239000011593 sulfur Substances 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- -1 silver halide Chemical class 0.000 description 15
- 229910052709 silver Inorganic materials 0.000 description 14
- 239000004332 silver Substances 0.000 description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 9
- 239000010931 gold Substances 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 2
- 229960001748 allylthiourea Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KWPNNZKRAQDVPZ-UHFFFAOYSA-N 1,3-bis(2-methylphenyl)thiourea Chemical compound CC1=CC=CC=C1NC(=S)NC1=CC=CC=C1C KWPNNZKRAQDVPZ-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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
- the present invention is concerned primarily with chemical sensitization apparently of the latter type.
- one object of our invention is to provide chemically sensitized emulsions of enhanced light sensitivity. Another object is to provide emulsions having sensitivity enhanced by the combined efiect of sulfur, gold and certain organic sulfide compounds. A further object is to provide the methods of augmenting emulsion sensitivity utilizing the novel combination of sensitizing agents. Another object is to provide photographic elements in which the novel emulsions are useful. Further objects of our invention will become apparent from consideration of the following description.
- the objects of our invention are accomplished by the incorporation into silver halide emulsions of a mixture of' (A) a sulfur-sensitizing agent such as disclosed in Sheppard U. S. Patents 1,574,944 granted March 2, 1926, and 1,623,499 granted April 5, 1927, e. g. thiourea, di-o-tolyl thiourea, allyl isothiocyanate, thiocarbanilide, sodium thiosulfate, thioacetamide and allyl thiourea, (B) a gold salt sensitizing agent such as disclosed in Waller 2 t and Dodd U. S. Patent 2,399,083 e. g.
- A a sulfur-sensitizing agent such as disclosed in Sheppard U. S. Patents 1,574,944 granted March 2, 1926, and 1,623,499 granted April 5, 1927, e. g. thiourea, di-o-tolyl
- gold chloride potassium chloroaurate or an alkali metal aurothiocyanate such as potassium aurothiocyanate
- an alkali metal aurothiocyanate such as potassium aurothiocyanate
- C either bis- (fi-aminoethyl) sulfide (NHzCH2CH2)2S and its watersoluble salts obtained from non-desensitizing acids such as the acetates, carbonates, sulfates and hydrochloride salts, or bis-(y-diethyl aminopropyl) disulfide at any stage in their preparation but preferably before digestion is complete.
- the quantity of sulfur, gold and organic sulfide sensitizing agents used in the emulsions is not especially critical and can be varied from the optimum amounts indicated in the following examples.
- the sensitizing agents are incorporated into the emulsions at any stage in their preparation but, preferably before digestion is complete. That is, the emulson can first be sensitized with a sulfur sensitizing agent and a gold salt sensitizing agent and then one of the organic sulfide sensitizing agents indicated, or the addition of the organic sulfide compound can be made prior to the'addition of p the gold salt sensitizing compound. However, it is preferred to partially digest the emulsion in the presence of the selected sulfur and gold sensitizing agents and to finish the emulsion by digesting it further after addition of the organic sulfide compound since the greatest One rather speed increases are obtained in this manner.
- Example 1 p A In a positive type of silver bromoiodide emulsion were incorporated 20 milligrams of allyl thiourea per mol of silver halide and 2 milligrams of potassium chloro aurate per mol of silver halide and the emulsion was digested for 61 minutes at 62 C. A sample of the emulsion was coated onto film base. i
- An emulsion was prepared as in B except using 600 milligrams of the sulfide per mol of silver'halide.
- Example 2 D To a fine-grained gelatino silver bromoiodide emulsion were added a sulfur sensitizer such as described above and a gold salt sensitizer such as described above. The emulsion was then digested to. optimum sensitivity and a sample coated on film.
- silver halide emulsions can be treated with the novel combination of sulfur, gold and organic sulfide sensitizing agents.
- the novel sensitizers may, in general, be employed in hydrophilic colloid emulsion vehicles; for example, gelatin, polyvinyl alcohol, partially hydrolyzed cellulose ester, such as cellulose acetate and copolymers of polyvinyl alcohol.
- the sensitizers are suitable 017 the well known types of silver chloride, silver bromide and silver iodide emulsions and emulsions containing mixtures of these halides, containing the usual emulsion addenda such as antifoggants, spreading agents, coupler compounds, etc.
- Such emulsions are suitable to use in forming single as well as multilayer film useful in color photography which customarily include on a support two or more emulsion layers sensitized to different regions of the visible spectrum and may or may not contain coupler compounds. According to our invention such color films carry at least one emulsion layer containing the mentioned combination of sensitizing agents.
- a light-sensitive photographic emulsion comprising silver halide sensitized with a sulfur sensitizing agent, a gold salt sensitizing agent and bis-(Y-diethylaminopropyl) disulfide.
Landscapes
- 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)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE523959D BE523959A (is") | 1952-11-08 | ||
| US319618A US2739060A (en) | 1952-11-08 | 1952-11-08 | Chemical sensitization of photographic emulsions |
| FR64779D FR64779E (fr) | 1952-11-08 | 1953-11-05 | Sensibilisation des émulsions photographiques et produits en résultant |
| GB30698/53A GB734472A (en) | 1952-11-08 | 1953-11-06 | Improvements in sensitized photographic emulsions |
| DEE8092A DE960871C (de) | 1952-11-08 | 1953-11-08 | Chemisch sensibilisiertes photographisches Material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US319618A US2739060A (en) | 1952-11-08 | 1952-11-08 | Chemical sensitization of photographic emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2739060A true US2739060A (en) | 1956-03-20 |
Family
ID=23243018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US319618A Expired - Lifetime US2739060A (en) | 1952-11-08 | 1952-11-08 | Chemical sensitization of photographic emulsions |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2739060A (is") |
| BE (1) | BE523959A (is") |
| DE (1) | DE960871C (is") |
| FR (1) | FR64779E (is") |
| GB (1) | GB734472A (is") |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3057725A (en) * | 1959-07-17 | 1962-10-09 | Eastman Kodak Co | Substituted disulfides as antifoggants for silver halide emulsions |
| US3419392A (en) * | 1965-02-24 | 1968-12-31 | Ilford Ltd | Thioether silver halide development accelerators |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2253144C1 (ru) * | 2003-11-03 | 2005-05-27 | Кемеровский государственный университет (КемГУ) | Способ химической сенсибилизации фотографической эмульсии |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2399083A (en) * | 1942-02-13 | 1946-04-23 | Ilford Ltd | Photographic materials |
| US2521926A (en) * | 1948-11-18 | 1950-09-12 | Eastman Kodak Co | Chemical sensitization of photographic emulsions |
| US2540086A (en) * | 1948-06-17 | 1951-02-06 | Silver halibe emulsions | |
| US2597856A (en) * | 1949-09-24 | 1952-05-27 | Eastman Kodak Co | Stabilization of photographic emulsions sensitized with gold compounds |
-
0
- BE BE523959D patent/BE523959A/xx unknown
-
1952
- 1952-11-08 US US319618A patent/US2739060A/en not_active Expired - Lifetime
-
1953
- 1953-11-05 FR FR64779D patent/FR64779E/fr not_active Expired
- 1953-11-06 GB GB30698/53A patent/GB734472A/en not_active Expired
- 1953-11-08 DE DEE8092A patent/DE960871C/de not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2399083A (en) * | 1942-02-13 | 1946-04-23 | Ilford Ltd | Photographic materials |
| US2540086A (en) * | 1948-06-17 | 1951-02-06 | Silver halibe emulsions | |
| US2521926A (en) * | 1948-11-18 | 1950-09-12 | Eastman Kodak Co | Chemical sensitization of photographic emulsions |
| US2597856A (en) * | 1949-09-24 | 1952-05-27 | Eastman Kodak Co | Stabilization of photographic emulsions sensitized with gold compounds |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3057725A (en) * | 1959-07-17 | 1962-10-09 | Eastman Kodak Co | Substituted disulfides as antifoggants for silver halide emulsions |
| US3419392A (en) * | 1965-02-24 | 1968-12-31 | Ilford Ltd | Thioether silver halide development accelerators |
Also Published As
| Publication number | Publication date |
|---|---|
| BE523959A (is") | |
| GB734472A (en) | 1955-08-03 |
| FR64779E (fr) | 1955-12-02 |
| DE960871C (de) | 1957-03-28 |
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