US2673152A - Azopyridine compounds as fog inhibitors for photographic emulsions - Google Patents
Azopyridine compounds as fog inhibitors for photographic emulsions Download PDFInfo
- Publication number
- US2673152A US2673152A US337234A US33723453A US2673152A US 2673152 A US2673152 A US 2673152A US 337234 A US337234 A US 337234A US 33723453 A US33723453 A US 33723453A US 2673152 A US2673152 A US 2673152A
- Authority
- US
- United States
- Prior art keywords
- azopyridine
- compounds
- emulsion
- silver halide
- fog
- 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 claims description 30
- VJTJVFFICHLTKX-UHFFFAOYSA-N dipyridin-2-yldiazene Chemical class N1=CC=CC=C1N=NC1=CC=CC=N1 VJTJVFFICHLTKX-UHFFFAOYSA-N 0.000 title claims description 5
- 239000003112 inhibitor Substances 0.000 title description 2
- -1 SILVER HALIDE Chemical class 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- VJTJVFFICHLTKX-BUHFOSPRSA-N (e)-dipyridin-2-yldiazene Chemical class N1=CC=CC=C1\N=N\C1=CC=CC=N1 VJTJVFFICHLTKX-BUHFOSPRSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000003927 aminopyridines Chemical class 0.000 description 2
- JOBHFKVEVOOQCR-UHFFFAOYSA-N bis(5-chloropyridin-2-yl)diazene Chemical compound N1=CC(Cl)=CC=C1N=NC1=CC=C(Cl)C=N1 JOBHFKVEVOOQCR-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 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
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 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
- MAXBVGJEFDMHNV-UHFFFAOYSA-N 5-chloropyridin-2-amine Chemical compound NC1=CC=C(Cl)C=N1 MAXBVGJEFDMHNV-UHFFFAOYSA-N 0.000 description 1
- IVILGUFRMDBUEQ-UHFFFAOYSA-N 5-iodopyridin-2-amine Chemical compound NC1=CC=C(I)C=N1 IVILGUFRMDBUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical class NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000003378 silver 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
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
Definitions
- This invention relates to fog-inhibiting agents and stabilizers for photographic emulsions and to photographic emulsions containing them.
- a further object is to provide antifogging agents which stabilize the initial .sensi- These ing into a silver halide emulsion small amounts of halogenated 2,2'-azopyridine compounds such as 5,5-dichloro-'2;2'-azop-yridine, 5,5"-7dibromo- 2,"2'-azopyridine, 5,5-diiodo-2;2-azopyridine, chloro-2,2 -azopyridine, 3,3 ,5 ,5" -.tetra'chl'oro -i2;2f azopyridine and 5,5'-dichloro-3,3-dimethyl-2;2'- azopyridine.
- U, S. Patent 2,273,502 discloses amino hydroxy pyrimidines as anti-fog such as 2,2'-azopyrimidine, 2,2'-azopyridine, 3,3- azoquinoline, 4,4-dimethyl-2,2'-azothiazole, and 6-azobenzimidazole have little or no anti-foggant genated amino pyridines, for example, .5-chloro- -amino pyridine and 3,5-ohloro-2-amino pyridine hydrochloride, in photographic developers
- our work shows that the halogenated amino pyridines such as 5-iodo-2-amino pyridine and 5- chloro-2-amino pyridine do not inhibit fog for- .our invention.
- the compounds invention such as 5,5-dichloro-2,2'-azopyridine do not function as anti-foggants when tures, however,
- a light-sensitive photographic emulsion comprising silverhalide and a halogenated 2,2- azopyr-idine in antifogg ant amoun 2.
- a light-sensitive photographic emulsion comprising silver halide and a member selected from the group consisting of 5,5'-dichloro-2,2'- azopyridine, 5,5-dibromo-2,2'-azopyridine, 5,5- diiodo-2 ,2 -azopyridine, 5-chloro-2,2' -azopyrldine, 3 ,3 ,5 ,5 -tetrachlo-2,2 -azopyridine, and 5,5-dichloro-3,3 -dimethyl-2,2'-azopyridine in 3.
- a light-sensitive photographic emulsion comprising silver halide and a chlorinated 2,2- azopyridine in antiioggant amount.
- a light-sensitive photographic emulsion comprising silver halide and a brominated 2,2- azopyridine in antifoggant amount.
- a light-sensitive photographic emulsion comprising silver halide and an iodated 2,2'-az0- pyridine in antifoggant amount.
- the fag-inhibiting agents which we have described may be used in various kinds of photographic emulsions. In addition to being useful inordinary non-sensitized emulsions they may also be used in orthochromatic, panchromatic If used with sensitizing dyes, they may be added to the emulsion before or after the dyes are added.
- Various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride and mixtures of these.
- the dispersing agents may be gelatin or other colloid such as collodion, ,al-
- a light-sensitive photographic emulsion comprising silver halide and 5.5-dibromo-2,2'- azopyridine in antifoggant amount.
- a light-sensitive photographic emulsion comprising silver halide and 5,5-diiodo-2,2'-azopyridine in antifoggant amount.
- a light-sensitive photographic comprising silver halide and 5-chloro-2,2-azopyridine in antifoggant amount.
- a light-sensitive photographic emulsion comprising silver halide and 3,3',5,5'-tetrachloro- 2,2'-'azopyridine in antifoggant amount.
- a light-sensitive photographic element comprising a silver halide emulsion layer and an organic colloid layer contiguous to said emulsion .layer, at least one of said layers containing a halogenated 2,2-azopyridine.
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)
- Pyridine Compounds (AREA)
Description
Patented Mar. 23, 1954 2,673,152 AZOPYRIDINE COMPOUNDS AS FOG IN HIBI- TORS FOR Charles F. H.
Conn.,
PHOTOGRAPHIC EMULSION S Allen and John R. Byers, Jr., Rochester, N. Y., and Robert H. Sprague, Portland,
assignors to Eastman Kodak Company, Rochester, ,N. Y.,.a corpo ration of New. Jersey No Drawing. Application February 16, 1953, Serial No. 337,234
11 Claims. 95--7) This invention relates to fog-inhibiting agents and stabilizers for photographic emulsions and to photographic emulsions containing them.
It is known that silver sensitized ing formula used and increases with the temperature and duration of development.
It is an object of the invention to :provide novel anti-fogging and fog-inhibiting compounds for emulsions. A further object is to provide antifogging agents which stabilize the initial .sensi- These ing into a silver halide emulsion small amounts of halogenated 2,2'-azopyridine compounds such as 5,5-dichloro-'2;2'-azop-yridine, 5,5"-7dibromo- 2,"2'-azopyridine, 5,5-diiodo-2;2-azopyridine, chloro-2,2 -azopyridine, 3,3 ,5 ,5" -.tetra'chl'oro -i2;2f azopyridine and 5,5'-dichloro-3,3-dimethyl-2;2'- azopyridine.
Similar azoxy compounds such as 4,4'-,dicliloro- 2, -azoxypyridine exhibit fog-inhibiting proper- J. Gen. Chem. (U. S. S. 'R.) (1940) C. A. .35, 40237 (1941.)
A wide variety of compounds have been used in photographic emulsions .to inhibit fog. For example, mercaptopyrimidine compound containing a 5-arylazo group are described by Sheppard et a1. U. S. Patent. 2,304,962 .for this purpose.
2 Similarly, Davey et a1. U, S. Patent 2,273,502 discloses amino hydroxy pyrimidines as anti-fogsuch as 2,2'-azopyrimidine, 2,2'-azopyridine, 3,3- azoquinoline, 4,4-dimethyl-2,2'-azothiazole, and 6-azobenzimidazole have little or no anti-foggant genated amino pyridines, for example, .5-chloro- -amino pyridine and 3,5-ohloro-2-amino pyridine hydrochloride, in photographic developers However, our work shows that the halogenated amino pyridines such as 5-iodo-2-amino pyridine and 5- chloro-2-amino pyridine do not inhibit fog for- .our invention. Moreover, the compounds invention such as 5,5-dichloro-2,2'-azopyridine do not function as anti-foggants when tures, however,
separate operations (1) the emulsidigestion or ripening of the silver halide, (2) the freeing of the emulsion .irom exsalts usually by washing, (3) the second digestion or after-ripening to obtain increased sensitivity. (Mees, "The Theory of the Photographic Process, 1942.) We prefer to add the fog-inhibiting agents after the final digestion or after-ripening although they may be added before digestion. The most'useful range of concentration of the fog inhibitor compounds of our emulsionsis from about 0.0025 to about 0.1 milligram per mol of silver halide in the emulsions as illustrated by .the following examples. The quantity will, of course, vary, for example, -.de-
V and X-ray emulsions.
was made employed, for samples A-I-I a high speed bromo-iodide emulsion, and for samples I-N a medium-speed bromoiodide emulsion. The samples were exposed as usual on an Eastman type 13 Sensitometer and developed for five minutes in a developer of the following composition:
V Grams Monomethyl paraminophenol sulfate 2.5 Sodium sulfite 3O Hydroquinone 2.5 Sodium metaborate Potassium bromide 0.5
Water te one liter In the case of the latent image keeping tests supplied below for samples A-H, it will be apparent that exposures were made on these samples in the same manner on the sensitcmeter but the exposed samples were incubated at 120 F. before 10 The test from which the following tabulation antifoggant amount.
We also contemplate as a part of our invention those cases where it is desirable to coat the antiioggant in a colloid layer such as gelatin on either or both sides of or also in a silver halide emulsion layer, so that the antifoggant is contiguous to the silver halide emulsion. In these cases'we use the same or a slightly greater ratio of the halogenated2,2-azopyridine compounds to silver halide than when the compounds are present in the emulsion.
What we claim is:
- 1. A light-sensitive photographic emulsion comprising silverhalide and a halogenated 2,2- azopyr-idine in antifogg ant amoun 2. A light-sensitive photographic emulsion comprising silver halide and a member selected from the group consisting of 5,5'-dichloro-2,2'- azopyridine, 5,5-dibromo-2,2'-azopyridine, 5,5- diiodo-2 ,2 -azopyridine, 5-chloro-2,2' -azopyrldine, 3 ,3 ,5 ,5 -tetrachlo-2,2 -azopyridine, and 5,5-dichloro-3,3 -dimethyl-2,2'-azopyridine in 3. A light-sensitive photographic emulsion comprising silver halide and a chlorinated 2,2- azopyridine in antiioggant amount.
4. A light-sensitive photographic emulsion comprising silver halide and a brominated 2,2- azopyridine in antifoggant amount.
5. A light-sensitive photographic emulsion comprising silver halide and an iodated 2,2'-az0- pyridine in antifoggant amount.
processing.
, Mgs. per Fresh Tests 1 wk. 120 F.
f Compound Emulsion Speed Gamma Fog Speed Gamma Fog A 3, 200 0. 97 0. 06 l, 400 0. 77 0 3, lOO 0. 93 05 2, 200 0. 87 16 2, 500 1. 00 04 2. 100 0.92 12 l, 950 1.11 05 1, 650 0. 96 ll 2, 650 0.99 05 2, 700 0. 85 14 2, 450 1. 02 05 2, 100 0. 97 12 2,000 1.06 05 1,750 0.97 12 2, 400 1. 03 05 l, 750 0.97 20 l, 620 0. 95 07 1,081) i 0.90 22 1, 600 0.90 06 l. 620 0. 94 16 do .r 1,550 0.88 .06 1,050 1.15 14 L 3,3-dimethyl-5,5-dichloro-2,2- 2 200 l. 06 .96 2, 500 1. 05 16 azopyridine. M do 6 1, 700 1. 11 O5 2, 450 1. 01 09 N 3,3',5,5 tetra chloro 2,2 azo 06 2, 550 1. l9 08 2, 350 0. 87 16 pyridine. r
Latent Image Keeping, 1 wk. 120 F.
- The fag-inhibiting agents which we have described may be used in various kinds of photographic emulsions. In addition to being useful inordinary non-sensitized emulsions they may also be used in orthochromatic, panchromatic If used with sensitizing dyes, they may be added to the emulsion before or after the dyes are added. Various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride and mixtures of these. The dispersing agents may be gelatin or other colloid such as collodion, ,al-
bumen, cellulose organic derivatives or synthetic resins.
50 comprising silver i 6. A light-sensitive photographic emulsion halide and 5,5'-dichloro-2,2'- azopyridine in antifoggant amount.
' '7. A light-sensitive photographic emulsion comprising silver halide and 5.5-dibromo-2,2'- azopyridine in antifoggant amount.
8. A light-sensitive photographic emulsion comprising silver halide and 5,5-diiodo-2,2'-azopyridine in antifoggant amount.
9. A light-sensitive photographic comprising silver halide and 5-chloro-2,2-azopyridine in antifoggant amount.
10. A light-sensitive photographic emulsion comprising silver halide and 3,3',5,5'-tetrachloro- 2,2'-'azopyridine in antifoggant amount.
11. A light-sensitive photographic element comprising a silver halide emulsion layer and an organic colloid layer contiguous to said emulsion .layer, at least one of said layers containing a halogenated 2,2-azopyridine.
CHARLES F. H. ALLEN. JOHN R. BYERS, JR- ROBERT H. SPRAGUE.
No references cited.
emulsion
Claims (1)
1. A LIGHT-SENSITIVE PHOTOGRAPHIC EMULSION COMPRISING SILVER HALIDE AND A HALOGENATED 2,2''AZOPYRIDINE IN ANTIFOGGANT AMOUNT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US337234A US2673152A (en) | 1953-02-16 | 1953-02-16 | Azopyridine compounds as fog inhibitors for photographic emulsions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US337234A US2673152A (en) | 1953-02-16 | 1953-02-16 | Azopyridine compounds as fog inhibitors for photographic emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2673152A true US2673152A (en) | 1954-03-23 |
Family
ID=23319679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US337234A Expired - Lifetime US2673152A (en) | 1953-02-16 | 1953-02-16 | Azopyridine compounds as fog inhibitors for photographic emulsions |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2673152A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2835581A (en) * | 1955-06-15 | 1958-05-20 | Eastman Kodak Co | Tetrazaindenes and photographic emulsions containing them |
| US3314790A (en) * | 1963-09-23 | 1967-04-18 | Eastman Kodak Co | Desensitizer for exposed silver halide emulsions |
-
1953
- 1953-02-16 US US337234A patent/US2673152A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2835581A (en) * | 1955-06-15 | 1958-05-20 | Eastman Kodak Co | Tetrazaindenes and photographic emulsions containing them |
| US3314790A (en) * | 1963-09-23 | 1967-04-18 | Eastman Kodak Co | Desensitizer for exposed silver halide emulsions |
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