US2919985A - Antifoggants and stabilizers for photographic silver halide emulsions - Google Patents
Antifoggants and stabilizers for photographic silver halide emulsions Download PDFInfo
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- US2919985A US2919985A US755149A US75514958A US2919985A US 2919985 A US2919985 A US 2919985A US 755149 A US755149 A US 755149A US 75514958 A US75514958 A US 75514958A US 2919985 A US2919985 A US 2919985A
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- silver halide
- emulsion
- stabilizers
- acid
- antifoggants
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- 239000000839 emulsion Substances 0.000 title claims description 33
- -1 silver halide Chemical class 0.000 title claims description 29
- 229910052709 silver Inorganic materials 0.000 title claims description 21
- 239000004332 silver Substances 0.000 title claims description 21
- 239000003381 stabilizer Substances 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000011161 development Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- ZEUUVJSRINKECZ-UHFFFAOYSA-N ethanedithioic acid Chemical compound CC(S)=S ZEUUVJSRINKECZ-UHFFFAOYSA-N 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YFBUDXNMBTUSOC-UHFFFAOYSA-N 1,4-dihydroquinoxaline-2,3-dithione Chemical compound C1=CC=C2NC(=S)C(=S)NC2=C1 YFBUDXNMBTUSOC-UHFFFAOYSA-N 0.000 description 2
- GRHQDJDRGZFIPO-UHFFFAOYSA-N 4-bromobutanoic acid Chemical compound OC(=O)CCCBr GRHQDJDRGZFIPO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [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
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- MVCPDOUDYOUTKS-UHFFFAOYSA-N propanedithioic acid Chemical compound CCC(S)=S MVCPDOUDYOUTKS-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 206010012289 Dementia Diseases 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BPOPGHPHBCLJOK-UHFFFAOYSA-N butanedithioic acid Chemical compound CCCC(S)=S BPOPGHPHBCLJOK-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005425 toluyl group Chemical group 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
- G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
Definitions
- the present invention relates to the use of antifogging and stabilizing agents for photographic silver halide emulsions and, more particularly, to the use of bis(carboxy lower alkyl-2,3-)quinoxalinyl dithio ethers, their salts and esters for such purpose.
- fog may be caused in a number of ways as, for example, by excessive ripening of the emulsion, during storage of the film particularly at elevated temperatures and humidity or by prolonged development of the exposed emulsion.
- R is hydrogen; an aliphatic radical such as alkyl, i.e., methyl, ethyl, propyl, butyl, amyl or the like; hydroxyalkyl, i.e., hydroxymethyl, hydroxyethyl and the like; carboxyalkyl, i.e., carboxymethyl, carboxyethyl and the like; aryl such as phenyl, toluyl, naphthyl, carboxyphenyl, sulfophenyl and the like; aralkyl such as benzyl or a monovalent cation such as sodium, potassium, silver, ammonium or the like and n is a whole number of from 1 to 3. Examples of compounds within the ambit of such formula which we have found to be effective are:
- the free acid thus produced may be converted to its salt by reaction with a water soluble compound containing the desired cation such as potassium carbonate, sodium carbonate, silver nitrate, ammonium carbonate or the like.
- a water soluble compound containing the desired cation such as potassium carbonate, sodium carbonate, silver nitrate, ammonium carbonate or the like.
- esters-are desired they are produced in the conventional manner by refluxing the free acid with the desired alcohol or phenol in the presence of hydrochloric acid.
- Coating finals are added to the emulsion just prior to coating on a suitable support such as glass, paper or film at a time when the emulsion has nearly obtained its maximum sensitivity. 7
- our antifoggants or stabilizers When used as ripening finals, our antifoggants or stabilizers are best employed in a concentration of 1 to 25 mgs. per .6 mol of silver halide and when used as coating finals in a concentration of 10 to 300 mgs. per .6 mol of silver halide.
- concentration used depends on the type of emulsion involved and it is recommended that the optimum concentration be determined from case to case.
- it is advantageous to apply the antifoggant in a layer adjacent to the silver. halide emulsion layer i.e., in an undercoating or in an antiabrasion gelatinsurface coating. In other cases, they may be applied in one or all processing baths.
- the antifoggants may be used in various photographic emulsions, e.g., non-sensitized, orthochromatic, panchromatic, X-ray emulsions, paper emulsions and color emulsions. They may be used alone or in combination with other antifoggants and stabilizers or in combination with sulfur, -reduction, -metal, and noble metal sensitizers or in combination with hydroxypolyethenoxy derivatives, i.e., those obtained by reacting ethylene oxide with an alcohol, phenyl, amine or the like. (See U.S.P. 1,970,578.)
- Example I exposed in a Type IIB Sensitometer and developed in a developer of the following composition:
- Example II The procedure was the same as in Example I excepting that there was used as the stabilizer 2,3-quinoxaline dithio propionic acid. The results were similar to those obtained in Example I.
- the stabilizer was prepared in the same manner as that of Example I while substituting p-bromopropionic acid for bromoacetic acid.
- Example III Exposed samples of a photographic film were developed for 12 minutes at 65 F. in a standard metol-hydroquinone developer. Two tests were made, one with a normal developing solution and one with a developer containing 500 mgs. of the stabilizer of Example I per one liter of developer. Sensitometric strips developed in the normal developer (control) for 12 minutes showed a fog of .30, whereas those strips which were developed in a developer containing the stabilizer had a fog of .20.
- Example IV The procedure was the same as in Example III excepting that there was used as the stabilizer 2,3-quinoxaline dithio butyric acid.
- Example IV The stabilizer of Example IV was prepared in the same way as that of Example I while replacing the bromoacetic acid by gamma-bromobutyric acid.
- a light-sensitive photographic material comprising a base and a light sensitive silver halide emulsion layer thereon, said light-sensitive material containing as an antifoggant and stabilizer a compound of the following formula:
- R is selected from the class consisting of hydrogen, an aliphatic radical, aryl, aralkyl and a moncwalent cation, and n is a whole number from 1 to 3.
- a light-sensitive photographic material comprising a base with a light-sensitive silver halide emulsion thereon, said emulsion containing as an antifoggant 2,3-quinoxaline dithio acetic acid.
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United. States Patent Fritz Del-sch and Millet R. De Angelus, Binghamton,
N.Y., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Application August 15, 1958 Serial No. 755,149
6 Claims. (CI. 96-66) The present invention relates to the use of antifogging and stabilizing agents for photographic silver halide emulsions and, more particularly, to the use of bis(carboxy lower alkyl-2,3-)quinoxalinyl dithio ethers, their salts and esters for such purpose.
Iti s known that light-sensitive emulsions such as gelatin silver halide emulsions have a tendency to fog. Such fog may be caused in a number of ways as, for example, by excessive ripening of the emulsion, during storage of the film particularly at elevated temperatures and humidity or by prolonged development of the exposed emulsion.
A great numberof substances have been described in the literature as being effective in preventing an increase in fog through stabilizing or controlling the keeping qualities of light-sensitive silver halide emulsions. Although many of these compounds have the ability to reduce fog tendencies and to improve stability, they are deficient in that they lower the sensitivity of the emulsions and in many cases reduce optical and dye sensitivity.
We have now found that bis(carboxy lower alkyl-2,3-) quinoxalinyl dithio ethers, their salts and esters are not only excellent stabilizers or antifogging agents for lightsensitive silver halide emulsions but, in addition, they have the ability of performing this function without lowering the sensitivity of the emulsion with which they are associated or without reducing the sensitivity of the emulsion to light of longer wave length attributable to the presence of sensitizing dyes.
The use of such compounds to inhibit fog and to stabilize silver halide emulsions, either by locating the same in the emulsion, in layers adjacent thereto or in processing baths for the emulsions, constitutes the purposes and objects of the present invention.
The stabilizers the use of which is contemplated herein may be represented by the following formula:
wherein R is hydrogen; an aliphatic radical such as alkyl, i.e., methyl, ethyl, propyl, butyl, amyl or the like; hydroxyalkyl, i.e., hydroxymethyl, hydroxyethyl and the like; carboxyalkyl, i.e., carboxymethyl, carboxyethyl and the like; aryl such as phenyl, toluyl, naphthyl, carboxyphenyl, sulfophenyl and the like; aralkyl such as benzyl or a monovalent cation such as sodium, potassium, silver, ammonium or the like and n is a whole number of from 1 to 3. Examples of compounds within the ambit of such formula which we have found to be effective are:
(l) 2,3-quinoxaline dithio acetic acid (2) The methyl, phenyl or ethyl ester of 2,3-quinoxaline dithio acetic acid (3) 2,3-quinoxaline dithio propionic acid and its sodium and silver salts The above compounds are prepared by refluxing 2,3- quinoxaline dithiol with a bromo aliphatic acid such as bromoacetic acid, fi-bromop-ropionic acid or gammabromobutyric acid in the presence of an acid binding agent such as sodium hydroxide, pyridine or the like. After cooling, the reaction mixture is acidified with a dilute acid and the solid which is precipitated is recrystallized from ethanol.
The free acid thus produced may be converted to its salt by reaction with a water soluble compound containing the desired cation such as potassium carbonate, sodium carbonate, silver nitrate, ammonium carbonate or the like.
If the esters-are desired, they are produced in the conventional manner by refluxing the free acid with the desired alcohol or phenol in the presence of hydrochloric acid.
Beneficial effects and fog reduction are obtained when solutions of the aforementioned compounds are incorporated in the silver halide emulsions as ripening finals or as coating finals. Ripening finals" are added dur ing the ripening or the sensitivity increasing stage of the emulsion making process. Suchradditions may be made before,'during or after the decomposition of the soluble silver salt such as silver nitrate by means of soluble halides such as potassium bromide in the presence of a colloidal carrier such as gelatine, .PVA, solubilized casein or albumin. 9
Coating finals are added to the emulsion just prior to coating on a suitable support such as glass, paper or film at a time when the emulsion has nearly obtained its maximum sensitivity. 7
When used as ripening finals, our antifoggants or stabilizers are best employed in a concentration of 1 to 25 mgs. per .6 mol of silver halide and when used as coating finals in a concentration of 10 to 300 mgs. per .6 mol of silver halide. The concentration used depends on the type of emulsion involved and it is recommended that the optimum concentration be determined from case to case. In some instances, it is advantageous to apply the antifoggant in a layer adjacent to the silver. halide emulsion layer, i.e., in an undercoating or in an antiabrasion gelatinsurface coating. In other cases, they may be applied in one or all processing baths. I
The antifoggants may be used in various photographic emulsions, e.g., non-sensitized, orthochromatic, panchromatic, X-ray emulsions, paper emulsions and color emulsions. They may be used alone or in combination with other antifoggants and stabilizers or in combination with sulfur, -reduction, -metal, and noble metal sensitizers or in combination with hydroxypolyethenoxy derivatives, i.e., those obtained by reacting ethylene oxide with an alcohol, phenyl, amine or the like. (See U.S.P. 1,970,578.)
The invention is further illustrated by the following examples but it is to be understood that the invention is not to be restricted thereto.
Example I exposed in a Type IIB Sensitometer and developed in a developer of the following composition:
The results of this procedure are tabulated as follows:
Relative Fog at 12 Oven Fog Quantity of Compound Used Speed Developat 6' Dement velopment 100 15 .30 400 mgs 100 15 17 The stabilizer used in this example was prepared as follows: To a solution containing 9 grams of sodium hydroxide in 175 milliliters of water were added 9.7 grams of 2,3-quinoxaline dithiol. To this solution in a small volume of water were added 13.9 grams of bromoacetic acid. The reactants were allowed to reflux for 3 hours. The reaction mixture was then cooled and acidified with concentrated hydrochloric acid to pH 2 and chilled in ice. The precipitate was collected, dissolved in ethanol, treated with charcoal and allowed to crystallize slowly overnight in a cooler. Recrystallization from ethanol gave 8 grams of a pure yellowishorange product.
Example II The procedure was the same as in Example I excepting that there was used as the stabilizer 2,3-quinoxaline dithio propionic acid. The results were similar to those obtained in Example I.
The stabilizer was prepared in the same manner as that of Example I while substituting p-bromopropionic acid for bromoacetic acid.
Example III Exposed samples of a photographic film were developed for 12 minutes at 65 F. in a standard metol-hydroquinone developer. Two tests were made, one with a normal developing solution and one with a developer containing 500 mgs. of the stabilizer of Example I per one liter of developer. Sensitometric strips developed in the normal developer (control) for 12 minutes showed a fog of .30, whereas those strips which were developed in a developer containing the stabilizer had a fog of .20.
Example IV The procedure was the same as in Example III excepting that there was used as the stabilizer 2,3-quinoxaline dithio butyric acid.
The results were substantially the same as those of Example III.
The stabilizer of Example IV was prepared in the same way as that of Example I while replacing the bromoacetic acid by gamma-bromobutyric acid.
Modifications of the invention will occur to persons skilled in the art. Thus, it is evident that in lieu of using the compounds of the examples, any of the compounds mentioned above may be employed with equally good results. We, therefore, do not intend to be limited in the patent granted except as necessitated by the appended claims.
We claim:
1. A light-sensitive photographic material comprising a base and a light sensitive silver halide emulsion layer thereon, said light-sensitive material containing as an antifoggant and stabilizer a compound of the following formula:
wherein R is selected from the class consisting of hydrogen, an aliphatic radical, aryl, aralkyl and a moncwalent cation, and n is a whole number from 1 to 3.
2. The article as defined in claim 1 wherein said antifoggant is located in the silver halide emulsion.
3. The article as defined in claim 1 wherein said antifoggant is located in a layer adjacent to said silver halide emulsion.
4. A light-sensitive photographic material comprising a base with a light-sensitive silver halide emulsion thereon, said emulsion containing as an antifoggant 2,3-quinoxaline dithio acetic acid.
5. The process of minimizing and preventing fog in light-sensitive silver halide materials comprising a base having a light-sensitive silver halide emulsion thereon which comprises exposing said emulsion and developing the same in a silver halide developer in the presence of an antifoggant and stabilizer of the following formula:
References Cited in the file of this patent UNITED STATES PATENTS Allen et al. Apr. 24, 1956 Murray et al. Jan. 14, 1958
Claims (1)
- 5. THE PROCESS OF MINIMIZING AND PREVENTING FOR IN LIGHT-SENSITIVE SILVER HALIDE MATERIALS COMPRISING A BASE HAVING A LIGHT-SENSITIVE SILVER HALIDE EMULSION THEREON WHICH COMPRISES EXPOSING SAID EMULSION AND DEVELOPMENT THE SAME IN SILVER HALIDE DEVELOPER IN THE PRESENCE OF AN ANTIFOGGANT AND STABILIZER OF THE FOLLOWING FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US755149A US2919985A (en) | 1958-08-15 | 1958-08-15 | Antifoggants and stabilizers for photographic silver halide emulsions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US755149A US2919985A (en) | 1958-08-15 | 1958-08-15 | Antifoggants and stabilizers for photographic silver halide emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2919985A true US2919985A (en) | 1960-01-05 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US755149A Expired - Lifetime US2919985A (en) | 1958-08-15 | 1958-08-15 | Antifoggants and stabilizers for photographic silver halide emulsions |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2919985A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3029237A (en) * | 1959-07-09 | 1962-04-10 | Bayer Ag | Quinoxolinyl thiophosphoric acid esters |
| US3091613A (en) * | 1958-07-10 | 1963-05-28 | Bayer Ag | 2, 3-dimercaptoquinoxaline derivatives |
| US5478721A (en) * | 1995-01-31 | 1995-12-26 | Eastman Kodak Company | Photographic elements containing emulsion stabilizers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2743181A (en) * | 1954-04-29 | 1956-04-24 | Eastman Kodak Co | Stabilized photographic silver halide emulsions |
| US2819965A (en) * | 1956-02-23 | 1958-01-14 | Eastman Kodak Co | Carboxymethylmercapto compounds as stabilizers for photographic emulsions |
-
1958
- 1958-08-15 US US755149A patent/US2919985A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2743181A (en) * | 1954-04-29 | 1956-04-24 | Eastman Kodak Co | Stabilized photographic silver halide emulsions |
| US2819965A (en) * | 1956-02-23 | 1958-01-14 | Eastman Kodak Co | Carboxymethylmercapto compounds as stabilizers for photographic emulsions |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3091613A (en) * | 1958-07-10 | 1963-05-28 | Bayer Ag | 2, 3-dimercaptoquinoxaline derivatives |
| US3029237A (en) * | 1959-07-09 | 1962-04-10 | Bayer Ag | Quinoxolinyl thiophosphoric acid esters |
| US5478721A (en) * | 1995-01-31 | 1995-12-26 | Eastman Kodak Company | Photographic elements containing emulsion stabilizers |
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