US3332776A - Fog reduction in photographic silver halide emulsions - Google Patents
Fog reduction in photographic silver halide emulsions Download PDFInfo
- Publication number
- US3332776A US3332776A US327082A US32708263A US3332776A US 3332776 A US3332776 A US 3332776A US 327082 A US327082 A US 327082A US 32708263 A US32708263 A US 32708263A US 3332776 A US3332776 A US 3332776A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- light
- antifoggant
- emulsion
- benzoic acid
- 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 66
- -1 silver halide Chemical class 0.000 title claims description 57
- 229910052709 silver Inorganic materials 0.000 title claims description 51
- 239000004332 silver Substances 0.000 title claims description 51
- 239000000463 material Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 16
- 239000005711 Benzoic acid Substances 0.000 description 8
- 235000010233 benzoic acid Nutrition 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- LMRKXSDOAFUINK-UHFFFAOYSA-N 3-chlorosulfonylbenzoic acid Chemical compound OC(=O)C1=CC=CC(S(Cl)(=O)=O)=C1 LMRKXSDOAFUINK-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 4
- PTCSSXYPZOFISK-UHFFFAOYSA-N 4-chlorosulfonylbenzoic acid Chemical compound OC(=O)C1=CC=C(S(Cl)(=O)=O)C=C1 PTCSSXYPZOFISK-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- ZRWICZHXYMHBDP-UHFFFAOYSA-N 2-chlorosulfonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(Cl)(=O)=O ZRWICZHXYMHBDP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000005425 toluyl group Chemical group 0.000 description 3
- 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 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N Benzyl benzoate Natural products C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-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
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229960002903 benzyl benzoate Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- VWYMBWGOJRULOV-UHFFFAOYSA-N 3-fluorosulfonylbenzoic acid Chemical compound OC(=O)C1=CC=CC(S(F)(=O)=O)=C1 VWYMBWGOJRULOV-UHFFFAOYSA-N 0.000 description 1
- QMWGSOMVXSRXQX-UHFFFAOYSA-N 3-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1 QMWGSOMVXSRXQX-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
- HWAQOZGATRIYQG-UHFFFAOYSA-N 4-sulfobenzoic acid Chemical compound OC(=O)C1=CC=C(S(O)(=O)=O)C=C1 HWAQOZGATRIYQG-UHFFFAOYSA-N 0.000 description 1
- USSHTWOXWQEPPI-UHFFFAOYSA-N 6-sulfonylcyclohexa-2,4-diene-1-carboxylic acid Chemical compound OC(=O)C1C=CC=CC1=S(=O)=O USSHTWOXWQEPPI-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WMGWLIAIMDFMIQ-UHFFFAOYSA-N sulfuroiodidic acid Chemical compound OS(I)(=O)=O WMGWLIAIMDFMIQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05G—CONTROL DEVICES OR SYSTEMS INSOFAR AS CHARACTERISED BY MECHANICAL FEATURES ONLY
- G05G7/00—Manually-actuated control mechanisms provided with one single controlling member co-operating with one single controlled member; Details thereof
- G05G7/02—Manually-actuated control mechanisms provided with one single controlling member co-operating with one single controlled member; Details thereof characterised by special provisions for conveying or converting motion, or for acting at a distance
- G05G7/04—Manually-actuated control mechanisms provided with one single controlling member co-operating with one single controlled member; Details thereof characterised by special provisions for conveying or converting motion, or for acting at a distance altering the ratio of motion or force between controlling member and controlled member as a function of the position of the controlling member
-
- 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
- the present invention relates to the employment of compounds which serve as antifoggant and stabilizing agents for photographic silver halide emulsions and, more par: ticularly, to the use of halogen sulfonyl benzoic acid, its salts and esters.
- the compounds which we use for this purpose may be generally described as halogen sulfonyl benzoic acids, their esters and alkali metal and ammonium salts.
- the addition of the above compounds as antifogging agents to the emulsions or to a layer adjacent to the emulsion or in a processing bath such as the developer, constitute the purpose and object of our invention.
- antifoggants the use of which is contemplated herein, may be typified by the following structural formula:
- X is halogen, such as chlorine, bromine, fluorine and iodine
- Y is hydrogen
- alkyl such as methyl, ethyl, propyl, butyl or the like
- aryl such as phenyl, toluyl, naphthyl or the like
- aralkyl such as benzyl, phenethyl or the like.
- m-chlorosulfonyl benzoic acid is prepared by reacting a mixture of benzoic acid and 5 mole equivalents of chlorosulfonic acid at a temperature of 125 C. for a period of one hour in an oil bath, until the evolution of hydrogen chloride ceases. After cooling, the mixture is poured over crushed ice and the solid mass ground under ice cold water, collected, washed with ice water and subsequently vacuum dried.
- the crude product, mchlorosulfonyl benzoic acid has a melting point of about 122 C. and after recrystallization from benzene the pure material is obtained in the form of colorless prisms having a melting point of 131 C. and an elemental analysis as follows:
- the above compound may also be obtained by long standing of the m-sulfo benzoic acid dichloride with water according'to the method of Limpricht and V. Usear, Ann. 106, 30.
- the p-chlorosulfonyl benzoic acid can be obtained by the oxidation of p-toluene sulfonyl chloride with CrO in acetic acid and acetic anhydride at a temperature of 4045 C. as indicated in CA. 1923 III 302.
- the p-chlorosulfonyl benzoic acid can be prepared in accordance with the procedures of Smiles and Harrison, J.C.S., 121, 2024 by heating 50 milliliters of chlorosulfonic acid and35 grams of anhydrous sodium salt of p-sulfo benzoic acid at a temperature of C. for a period of about one hour.
- the resultant liquid is cooled and poured slowly over crushed ice, the colorless product cooled, washed with ice water and air dried to provide a yield of crude product of from 30'3S grams of p-chlorosulfonyl benzoic acid.
- the product is moderately soluble in hot acetone and can be recrystallized therefrom in the form of colorless needles having a melting point with decomposition of about 235 C.
- the product Upon analysis, the product has the following properties:
- the method of Smiles and Harrison is suitable for preparing p-halogen sulfonyl benzoic acid compounds other than the chloro compound by replacing the chlorosulfonic acid by bromosulfonic, iodosulfonic acid, or the like.
- the o-chlorosulfonyl benzoic acid can be prepared by the same method as the para derivative in accordance with the procedure of Smiles and Harrison, J.C.S. 121, 2024.
- the product is isolated in acetone instead of water since it is very unstable in water even at C.
- the addition of the antifoggants can be made before, during or after the addition of the soluble silver salt to the soluble halide in the presence of a suitable carrier or colloid such as gelatin, polyvinyl alcohol, polyvinyl-pyrrolidone, solubilized casein, albumin and the like.
- a suitable carrier or colloid such as gelatin, polyvinyl alcohol, polyvinyl-pyrrolidone, solubilized casein, albumin and the like.
- the amount of antifogging agent employed as additives to the light-sensitive emulsions varies from about 0.02 to about 20.0 milligrams of antifoggant per 0.6 mole of silver halide.
- antifogging agents When the antifogging agents are employed as ripening finals it has been found advantageous to employ them in amounts in the range of from about 0.02 to about 5.0 milligrams per 0.6 mole of silver halide whereas, when the antifogging agents are employed in coating finals, it has been found advantageous to employ amounts in the range of from about 1.0 to about milligrams of antifoggant per 0.6 mole of silver halide.
- antifoggants can be employed also in various kinds of photographic emulsions such as non-sensitized emulsions, orthochromatic emulsions, panchromatic emulsions, X-ray emulsions, paper emulsions, color emulsions and the like.
- the antifogging agents of the invention in adjacent layers, for example, in a separate undercoating layer or in the antiabrasion gelatin surface.
- antifogging agents of the invention can be compatibly employed in combination with other known antifoggants and stabilizers; with sulfur-, reduction and metal-, and noble metal sensitizers as well as in combination with polyoxyalkylene polyols, their derivatives; polyvinyl-pyrrolidones and other accelerators.
- Example I A silver halide emulsion in gelatin containing 2% silver iodide and 98% silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. It was then readied for coating, finals were added such as sensitizing dyes and hardening agents. A 0.01% solution of m-chlorosulfonyl benzoic acid was added to the emulsion as an antifoggant and stabilizer. The emulsion samples contained about 0.6 mole of silver halide. The so-prepared emulsion samples were coated on a suitable cellulose ester base and dried. Samples of these film coatings were then exposed in a Type IB Sensitometer and developed in a developer of the following composition:
- Example II Exposed samples of a photographic film were developed for twelve minutes at 65 F. in a standard metol-hydroquinone developer. Two tests were made, one with the normal developing solution and one with a developer containing 4 mg. of m-chlorosulfonyl benzoic acid per one liter of developer. Sensitometric strips, developed in the normal developer (control) for twelve minutes showed a fog of .30, whereas those strips which were developed in the developer containing the antifoggant had a fog of .18.
- Example III A silver halide emulsion in gelatin containing 2% silver iodide and 98% silver bromide was coated on film base in a manner known to the art. After the coating, an aqueous gelatin solution containing 20 grams gelatin in 1 liter H 0 and 80 mg. m-chlorosulfonyl benzoic acid was coated thereon as an antiabrasion layer. After drying, film samples were exposed and processed as described in Example I. The samples exhibited a relative speed of 100 and a fog of .12 compared with type coating of the above emulsion having an antiabrasion layer similar to that described above, but lacking the antifoggant and having a speed of 100 and a fog of .18.
- Example IV The procedure is the same as in Example I excepting that the antifoggant used was o-brornosulfonyl benzoic acid. The results were substantially the same.
- Example V The procedure was the same as in Example III excepting that the antifoggant used was p-chlorosulfonyl ethyl benzoate. Equally good results were thus obtained.
- a light-sensitive photographic material comprising a light-sensitive silver halide emulsion, a carrier therefor and an antifoggant characterized by the general formula:
- SiOZX COOY wherein X represents a halogen atom selected from the group consisting of chlorine, bromine, fluorine and iodine and Y represents a member selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, toluyl naphthyl, benzyl, phenethyl groups, alkali metal and the ammonium radical, the amount of antifoggant being from 0.02 to 200 milligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emul- SlOl'l.
- antifoggant located in the silver halide emulsion, the amount of antifoggant being from 0.02 to 20 milligrams per 0.6 mole of silver halide contained in said fight-sensitive silver halide emulsion.
- a light-sensitive photographic material comprising a light-sensitive silver halide emulsion, a carrier therefor, said emulsion containing, as an antifoggant, a chlorosulfonyl benzoic acid, the amount of antifoggant being from 0.02 to 20 milligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emulsion.
- a light-sensitive photographic material comprising a light-sensitive silver halide emulsion, a carrier therefor, said emulsion containing, as an antifoggant, p-chlorosulfonyl benzoic acid, the amount of antifoggant being from 0.02 to 20 milligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emulsion.
- a light-sensitive photographic material comprising a light-sensitive silver halide emulsion, a carrier therefor, said emulsion containing, as an antifoggant, o-chlorosulfonyl benzoic acid, the amount of antifoggant being from 0.02 to 20 milligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emulsion.
- a light-sensitive photographic material comprising a light-sensitive silver halide emulsion, a carrier therefor, said emulsion containing, as an antifoggant, an alkali metal salt of a halosulfonyl benzoic acid, the amount of antifoggant being from 0.02 to 20 milligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emulsion.
- a light-sensitive photographic material comprising a light-sensitive silver halide emulsion, a carrier therefor, said emulsion containing, as an antifoggant, an ammonium salt of halosulfonyl benzoic acid, the amount of antifoggant being from 0.02 to 20 milligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emulsion.
- a light-sensitive photographic material comprising a light-sensitive silver halide emulsion, a carrier therefor, said emulsion containing, as an antifoggant, a halosulfonyl benzoic acid, the amount of antifoggant being from 0.02 to 20 mliligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emulsion.
- a light-sensitive photographic material comprising a light-sensitive silver salide emulsion, a carrier therefor, said emulsion containing, as an antifoggant, a hydrocarbon ester of a halosulfonyl benzoic acid, the amount of antifoggant being from 0.02 to 20 milligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emulsion.
- a 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 to light and developing the same in the presence of an antifoggant characterized by the general formula:
- X represents a halogen atom selected from the group consisting of chlorine, bromine, fluorine and iodine
- Y represents a member selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, toluyl, naphthyl, benzyl, phenethyl groups, alkali metal and the ammonium radical, the amount of antifoggant being from 0.02 to 200 milligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emulsion.
- X represents a halogen atom selected from the group consisting of chlorine, bromine, fluorine and iodine
- Y represents a member selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, toluyl, naphthyl, benzyl, phenethyl groups, alkali metal and the ammonium radical, the amount of antifoggaut being from 0.02 to 200 milligrams per 0.6 mole of silver halide contained in said light-sensitive silver halide emulsion.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Automation & Control Theory (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US327082A US3332776A (en) | 1963-11-29 | 1963-11-29 | Fog reduction in photographic silver halide emulsions |
| GB47758/64A GB1080425A (en) | 1963-11-29 | 1964-11-24 | Improvements in or relating to photographic materials |
| BE656351D BE656351A (fr) | 1963-11-29 | 1964-11-27 | |
| FR996742A FR1415281A (fr) | 1963-11-29 | 1964-11-28 | Réduction du voile dans les émulsions photographiques d'halogénure d'argent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US327082A US3332776A (en) | 1963-11-29 | 1963-11-29 | Fog reduction in photographic silver halide emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3332776A true US3332776A (en) | 1967-07-25 |
Family
ID=23275075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US327082A Expired - Lifetime US3332776A (en) | 1963-11-29 | 1963-11-29 | Fog reduction in photographic silver halide emulsions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3332776A (fr) |
| BE (1) | BE656351A (fr) |
| FR (1) | FR1415281A (fr) |
| GB (1) | GB1080425A (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410619A (en) * | 1981-04-11 | 1983-10-18 | Mitsubishi Paper Mills, Ltd. | Photographic material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2725295A (en) * | 1952-07-17 | 1955-11-29 | Eastman Kodak Co | Hardening of gelatin with organic acid chlorides |
| US2897081A (en) * | 1957-12-30 | 1959-07-28 | Gen Aniline & Film Corp | Antifogging agent and bactericide for photographic emulsions |
| DE1130590B (de) * | 1960-01-19 | 1962-05-30 | Gevaert Photo Prod Nv | Verfahren zum Haerten von Proteinen |
| US3128187A (en) * | 1961-02-08 | 1964-04-07 | Eastman Kodak Co | Antifoggants for photographic silver halide emulsions |
-
1963
- 1963-11-29 US US327082A patent/US3332776A/en not_active Expired - Lifetime
-
1964
- 1964-11-24 GB GB47758/64A patent/GB1080425A/en not_active Expired
- 1964-11-27 BE BE656351D patent/BE656351A/xx unknown
- 1964-11-28 FR FR996742A patent/FR1415281A/fr not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2725295A (en) * | 1952-07-17 | 1955-11-29 | Eastman Kodak Co | Hardening of gelatin with organic acid chlorides |
| US2897081A (en) * | 1957-12-30 | 1959-07-28 | Gen Aniline & Film Corp | Antifogging agent and bactericide for photographic emulsions |
| DE1130590B (de) * | 1960-01-19 | 1962-05-30 | Gevaert Photo Prod Nv | Verfahren zum Haerten von Proteinen |
| US3149974A (en) * | 1960-01-19 | 1964-09-22 | Gevaert Photo Prod Nv | Gelatino silver halide emulsion layers containing sulfofluoride hardeners |
| US3128187A (en) * | 1961-02-08 | 1964-04-07 | Eastman Kodak Co | Antifoggants for photographic silver halide emulsions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410619A (en) * | 1981-04-11 | 1983-10-18 | Mitsubishi Paper Mills, Ltd. | Photographic material |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1415281A (fr) | 1965-10-22 |
| GB1080425A (en) | 1967-08-23 |
| BE656351A (fr) | 1965-03-16 |
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