US2472631A - Palladium complexes as photographic emulsion stabilizers - Google Patents
Palladium complexes as photographic emulsion stabilizers Download PDFInfo
- Publication number
- US2472631A US2472631A US13352A US1335248A US2472631A US 2472631 A US2472631 A US 2472631A US 13352 A US13352 A US 13352A US 1335248 A US1335248 A US 1335248A US 2472631 A US2472631 A US 2472631A
- Authority
- US
- United States
- Prior art keywords
- fog
- emulsion
- silver halide
- photographic emulsion
- palladium complexes
- 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 34
- 239000003381 stabilizer Substances 0.000 title description 3
- 150000002940 palladium Chemical class 0.000 title 1
- 229910052709 silver Inorganic materials 0.000 description 16
- 239000004332 silver Substances 0.000 description 16
- -1 silver halide Chemical class 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 11
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 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
- This invention relates to fog-inhibiting agents and stabilizers for photographic emulsions and to photographic emulsion-s containing them.
- Photographic fog is of two types: local and general. Local fog is formed by exposure of the film or plate at undesired points as by a light leak in the camera. General fog is formed in a number of ways. It may be caused by. the
- emulsion such as conditions of high temperature or humidity or unusually long time of storage.
- the nature of the emulsion may also produce general fog as well as the conditions of development of the emulsion as by development for protracted periods of time or at temperatures above normal.
- We are primarily concerned with fog and sensitivity changes produced in films or plates on development after storage under adverse conlcjitirons of high temperature and humidity or General fog and loss of sensitivity of the emulsion are especially likely to occur when the sensitive material is stored under conditions other than ideal, that is, under conditions of high temperature and humidity as in tropical regions.
- a further object is to provide antifogging agents which stabilize the initial sensitivity of the emulsion.
- a still further object is to provide anti-fogging agents which improve the keeping of the emulsion in tropical regions.
- an anionic palladium complex salt such as alkali metal or alkaline earth metal thiocyanato palladites, nitritopalladites, bromo-nitritopalladates, and ammonlum nitritopalladite.
- potassium thiocyanato palladite mPd(CNS)4; calcium thiocyanato palladite, CaPd(CNS)4; potassium nitrito palladite, K2Pd(NO2)4; barium nitrito palladite, BaPd(NO2)4; potassium bromonitrito palladate, K2PdBr2(NO2)4, or ammonium nitritopalladite, (NH4)2Pd(NO2)4.
- Other similar anionic palladium complexes which have not been satisfactory, particularly because of fog- 5 Claims.
- "(01. 95-7) -2 ging properties or desensitizing action on the photographic emulsion include ammonium and potassium cyano palladites and ammonium thiocyanato palladite.
- the object of our invention is to maintain the sensitivity and fog of silver halide emulsion at or close to initial optimum values under keeping conditions of high temperature and humidity.
- the fog inhibitors which we propose to use are added to the emulsion during the process of manufacture to avoid loss of sensitivity and to inhibit the growth of incubation or keeping fog with passage of time under non-ideal conditions of storage.
- a solution of the compounds of the invention when added in suitable concentration before coating to unsensitized or optically sensitized photographic emulsions does notaiiect appreciably the sensitometric values for sensitivity and fog when measurements are made soon after coating.
- sensitometric measurements are made after appreciable intervals of time under tropical or dry conditions of storage at elevated temperatures, however, the compounds stabilize photographic speed and in certain cases maintain fog at a low level.
- the preparation of silver halide emulsions involves three separate operations, (1) the emulsification and digestion or ripening of the silver halide, (2) the freeing of the emulsion from excess soluble salts usually by washing, (3) the second digestion or after-ripening to obtain increased sensitivity (Mees, The Theory of the Photographic Process, 1942).
- the most useful concentration range of fog inhibitor is from 0.26 to 3.9 gm. of fog inhibitor per kilogram of silver nitrate used in making the emulsion and converted to silver halide. This amount will vary, e. g., depending upon the particular silver halide used.
- the antifoggant and stabilizing action was determined by incubation of the emulsions under simulated tropical conditions and also by incubation in dry heat at F. for various lengths of time from 6 days to 2 months. The results of these ageing tests are tabulated below and are compared with the initial speed, gamma and fog of the emulsion without th stabilizing compounds.
- the tests from which the following tabulation was made used a high-speed orthochromatic negative type of emulsion exposed on an EastmanfI ype sensitometer' and develq oped for five minutes in a developer of the following composition:
- the fog inhibitor is dissolved in water follows:
- Examples of the method oi preparatiomand use of the compounds orthemvehuta are-elven 40
- the compound was added to the emulSiondn'the-" quantity shown in the tabla above and the emiilsion containing the usual 'hardener and 1 sensitizew was coa'ted on a glass*plate driei exposed and developed.
- the emulsion is coated ona suitable supv 1 por-t, glass;-fi1m,- or -other,- and dried inanormal fashion; 7 I
- the compounds maylbe used in a colloid layer-suchasa geiauri' subbin'gor overcoating layer contiguous" tofadJ'acent to, or n contact with the emulsionla'yei'.
- a colloid layer suchasa geiauri' subbin'gor overcoating layer contiguous" tofadJ'acent to, or n contact with the emulsionla'yei'.
- the compounds stabili'z'e'thfe emulsiori'when it is aged over long periods of time especially under non-ideal con-- ditibris'of temperature and humidity.
- theamount of the compound per unit area should be the -same; per kilogram" of silv'er nitifat convertedt silver halide, as would be used 3 ili'tll' saini'llfiit' area of the emulsion if'the com pouriaweredn the emulsiofi'la'yerl v
- the fog' inhibitih'g ,age'rits' whichwe have' de-" scribed" may .bdu'sed iii va ious kinds of hoto graphic emulsions.
- the dispersing agents may be gelatin or other colloid such as collodion, albumen, cellulose derivatives, or synthetic resins.
- an anionic palladium complex salt selected from the group consisting of alkali metal and alkaline earth metal thiocyanato palladites, alkali metal and alkaline earth metal nitritopalladites, alkali metal and alkaline earth metal bromo-nitritopalladates and ammonium nitritopalladite.
- a silver halide emulsion containing an alkali metal thiocyanato palladite 1.
- a silver halide emulsion containing an alkali metal nitritopalladite 3.
- a silver halide emulsion containing ammonium nitritopalladite 4.
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE487512D BE487512A (enrdf_load_stackoverflow) | 1948-03-05 | ||
| US13352A US2472631A (en) | 1948-03-05 | 1948-03-05 | Palladium complexes as photographic emulsion stabilizers |
| FR982271D FR982271A (fr) | 1948-03-05 | 1949-03-02 | Nouveaux agents antivoile et leurs procédés de préparation |
| GB6142/49A GB657805A (en) | 1948-03-05 | 1949-03-07 | Improvements in sensitive photographic materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13352A US2472631A (en) | 1948-03-05 | 1948-03-05 | Palladium complexes as photographic emulsion stabilizers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2472631A true US2472631A (en) | 1949-06-07 |
Family
ID=21759517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13352A Expired - Lifetime US2472631A (en) | 1948-03-05 | 1948-03-05 | Palladium complexes as photographic emulsion stabilizers |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2472631A (enrdf_load_stackoverflow) |
| BE (1) | BE487512A (enrdf_load_stackoverflow) |
| FR (1) | FR982271A (enrdf_load_stackoverflow) |
| GB (1) | GB657805A (enrdf_load_stackoverflow) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4102312A (en) * | 1975-10-30 | 1978-07-25 | Toyota Jidosha Kogyo Kabushiki Kaisha | Thermally developable light-sensitive materials |
| US4617258A (en) * | 1982-04-09 | 1986-10-14 | Konishiroku Photo Industry Co., Ltd. | Silver halide photographic material |
| US6197485B1 (en) * | 1992-11-12 | 2001-03-06 | Minnesota Mining & Manufacturing Company | Photographic assemblage comprising a silver halide photographic element sealed in a closed vessel |
| JP3401696B2 (ja) | 1995-10-03 | 2003-04-28 | コニカ株式会社 | ハロゲン化銀写真感光材料及びその処理方法 |
| US20050123867A1 (en) * | 2003-12-04 | 2005-06-09 | Eastman Kodak Company | Silver halide elements containing activated precursors to thiocyanato stabilizers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1120580A (en) * | 1913-09-22 | 1914-12-08 | William Willis | Sensitive photographic paper and process of making the same. |
| US1120429A (en) * | 1913-09-22 | 1914-12-08 | William Willis | Process for the production of photographic prints. |
-
0
- BE BE487512D patent/BE487512A/xx unknown
-
1948
- 1948-03-05 US US13352A patent/US2472631A/en not_active Expired - Lifetime
-
1949
- 1949-03-02 FR FR982271D patent/FR982271A/fr not_active Expired
- 1949-03-07 GB GB6142/49A patent/GB657805A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1120580A (en) * | 1913-09-22 | 1914-12-08 | William Willis | Sensitive photographic paper and process of making the same. |
| US1120429A (en) * | 1913-09-22 | 1914-12-08 | William Willis | Process for the production of photographic prints. |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4102312A (en) * | 1975-10-30 | 1978-07-25 | Toyota Jidosha Kogyo Kabushiki Kaisha | Thermally developable light-sensitive materials |
| US4617258A (en) * | 1982-04-09 | 1986-10-14 | Konishiroku Photo Industry Co., Ltd. | Silver halide photographic material |
| US6197485B1 (en) * | 1992-11-12 | 2001-03-06 | Minnesota Mining & Manufacturing Company | Photographic assemblage comprising a silver halide photographic element sealed in a closed vessel |
| JP3401696B2 (ja) | 1995-10-03 | 2003-04-28 | コニカ株式会社 | ハロゲン化銀写真感光材料及びその処理方法 |
| US20050123867A1 (en) * | 2003-12-04 | 2005-06-09 | Eastman Kodak Company | Silver halide elements containing activated precursors to thiocyanato stabilizers |
Also Published As
| Publication number | Publication date |
|---|---|
| FR982271A (fr) | 1951-06-08 |
| BE487512A (enrdf_load_stackoverflow) | |
| GB657805A (en) | 1951-09-26 |
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