US3046130A - Photographic materials containing a chemical sensitizer - Google Patents
Photographic materials containing a chemical sensitizer Download PDFInfo
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- US3046130A US3046130A US28525A US2852560A US3046130A US 3046130 A US3046130 A US 3046130A US 28525 A US28525 A US 28525A US 2852560 A US2852560 A US 2852560A US 3046130 A US3046130 A US 3046130A
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- Prior art keywords
- silver halide
- emulsion
- photographic
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- Prior art date
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- 239000000463 material Substances 0.000 title description 15
- 239000000126 substance Substances 0.000 title description 2
- -1 SILVER HALIDE Chemical class 0.000 claims description 43
- 229910052709 silver Inorganic materials 0.000 claims description 34
- 239000004332 silver Substances 0.000 claims description 34
- 230000001965 increasing effect Effects 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 235000006708 antioxidants Nutrition 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 description 40
- 239000002585 base Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 125000000623 heterocyclic group Chemical group 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 150000002790 naphthalenes Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 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 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-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
- 239000003381 stabilizer Substances 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ZLKBPNVQFKCDEJ-UHFFFAOYSA-N 2-methyloxirane hydroiodide Chemical compound CC1OC1.I ZLKBPNVQFKCDEJ-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
- 206010034960 Photophobia Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 150000001420 substituted heterocyclic compounds Chemical class 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/36—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/28—Sulfur atoms
-
- 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
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
Definitions
- This invention relates to photographic materials. More particularly, this invention relates to photographic materials sensitized by means of water soluble heterocyclic compotmds which are substituted by a polyoxyalkylene chain.
- polyalkylene oxides such as polyoxyethylene and polyoxypropylene increase the speed of silver halide emulsions. It has also been observed that condensation products of alkylene oxides with amines, carboxylic acids, alcohols, amides or phenols (made according to U.S. Patents 1,970,578 and 2,213,- 477) and dicyclohexylol-dialkyl methane (see U.S. Patent 2,240,472) have been used as sensitizers.
- the polyalkylene oxides or the alkylene oxide condensation products should have a molecular weight of at least 300 and preferably 1,500 to 4,000 or more.
- a further object of this invention is to provide a photographic film comprising a layer containing a water-soluble polyoxyalkylene derivative of a hydroXyor mercaptosubstituted azole in which the polyoxyalkylene chain replaces the hydrogen atom of the mercapto group.
- the fogging of photographic film having a coating of a silver halide emulsion and containing the novel sensitizer of our invention may, therefore, be controlled by the use of the conventional antifoggants and stabilizer used in the photographic art; and the use of a special type of antifoggant to prevent fogging of an emulsion containing conventional polyoxyalkylenes such as those disclosed in U.S. Patents 2,704,716, 2,716,062 and 2,728,666 becomes unnecessary.
- polyoxyalkylene substituted heterocyclic compounds contemplated for use herein have the following general formula:
- heterocyclic polyoxyalkylene compounds are produced by introducing hydroxy aliphatic ether radlcals into 2hydroxyor Z-mercapto-substituted azoles according to the procedure described in United States Patent act . a t
- the above described heterocyclic compounds are condensed with hydroxy compounds such as ethylene oxide,
- the increase of effective sensitivity of photographic silver halide emulsions with the polyoxyalkylene derivatives of the Z-mercaptoor 2hydroxy-substituted heterocyclics can be obtained in a number of ways. They may be added to an undercoating, to a middle coating, to an overcoating or to a surface coating prior to the coating operation. If desired, they may be added during the actual preparation of the emulsion, either before or after washing of the emulsion.
- the speed and sensitivity increasing agents of our invention may be used in various types of photographic emulsions; e.g., nonsensitized emulsions, orthochromatic,
- sensitizing dyes they may be added to the emulsion before or after the dyes are added.
- Various silver salts may be used as a sensitive element, such as silver bromide, silver iodide, silver chloride or mixed silver halides.
- These hydroxy-substituted ether or thioether derivatives of heterocyclic compounds may be used in emulsions intended for color photography, e.g., emulsions containing color-forming components.
- the carrier in the photographic emulsion may be gelatin or other colloids such as collodion, albumen, cellulose derivatives, polyvinyl alcohol or synthetic resins.
- the emulsion containing our novel sensitizer may be coated on any conventional base, such as paper, glass, cellulose ester such as cellulose acetate, cellulose ethers and others.
- the amounts of sensitivity increasing agents used per kilogram of emulsion range from 15 to 500 milligrams per kilogram of liquid emulsion.
- the amounts of sensitivity increas ing agents range from 25 to 500 milligrams per mole of silver halide.
- the sensitivity increasing agents of our invention can also be added to pre-bath solutions or to standard developer solutions.
- developer solutions contain, in addition to the speed increasing agent, a developing agent such as metol, hydroquinone l-phenyl 3 pyrazolidone (phenidone); an alkali such as sodium or potassium carbonate; a preservative or anti-oxidant such as sodium sulfite; and an antifoggant such as potassium bromide.
- a developing agent such as metol, hydroquinone l-phenyl 3 pyrazolidone (phenidone)
- an alkali such as sodium or potassium carbonate
- a preservative or anti-oxidant such as sodium sulfite
- an antifoggant such as potassium bromide.
- the amounts of speed increasing agents used range from 0.3 to 6.0 grams per liter of developer solution.
- Example I s i G-S-QHzCI-Ia-(CHiCH9O) 1-I ⁇ NH
- a silver halide emulsion in gealtin containing 4 percent silver iodide and 96 percent silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. It was then readied for coating on film base, that is, melted at 40 C.; and the necessary coating finals were added, such as sensitizing dyes, stabilizers and hardeners.
- a percent aqueous solution of the reaction product of Z-mercaptobenzimidazole and 6 moles of ethylene oxide was prepare, and 10 cc.
- the ethylene oxide derivative of Z-mercaptobenzimidazole which served as a sensitizer was prepared as follows: 50 grams of Z-mercaptobenzimidazole was mixed with 0.5 gram of potassium hydroxide which had been dissolved in a minimum amount oi: water; the mass was heated to C.; ethylene oxide was passed through until 6 moles of ethylene oxide had been taken up.
- Example II The procedure was the same as in Example I excepting that there was used the reaction product of Z-mercaptobenzimidazole and trimethylene chlorhydrine which was then condensed with 8 moles of ethylene oxide. The results were similar to those obtained in Example I.
- Example III a tea Pg The procedure was the same as in Example I excepe ing that the reaction product of 2-hydroxybenzothiazole and 4 moles of propylene oxide iodide was used. The results were similar to those obtained in Example I.
- the compound was prepared by heating under reflux 1 mole of 2-hydroxybenzothiazole and 1 mole of propylene oxide for 1 hour using a small amount of potassium hydroxide. Additional increments of propylene oxide were added while heating and refluxing continued until a total of 4 moles of propylene oxide had been consumed.
- Example V One kilo of a silver halide emulsion in gelatin containing 4 percent silver iodide and 96 percent silver bromide was coated on film base in a manner known to the art. After the coating was performed, an aqueous gelatin solution containing 20 grams of gelatin per liter and 20 milligrams of the polyoxyethylene derivative of 2-mercaptobenzimidazole of Example I was coated thereon as an anti-abrasion layer. After drying, film samples were exposed and processed as described in Example I.
- the samples described exhibited a relative speed of 150 with a fog of .22 as compared with a type coating of the same emulsion having an anti-abrasion layer similar to that described above, but lacking the speed increasing additive and having a speed of 100 and a fog of .20.
- Example Vl Several samples of a conventional photographic film were exposed in a type II-B sensitometer and then divided into two groups. One group of samples was developed for twelve minutes at 68 F. in a standard metolhydroquinone developer as described in Example I. The other group of samples was developed for the same length of time and at the same temperature as the first group in a metol-hydroquinone developer which had been prepared by adding to 1 liter of the developer described in Example I, 2 grams of the reaction product of ethylene oxide and Z-mercaptobenzimidazole. It was found that the samples developed in the standard developer had a relative speed of 100 whereas the samples developed in the developer containing the novel sensitivity increasing agent of our invention showed a relative speed of 175 without an increase in fog.
- A is a member selected from the group consisting of oxygen and sulfur; R and R are alkylene groups containing from 2 to 3 carbon atoms; X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino and vinylene; Z represents the atoms necessary to complete an aromatic ring system of the benzeneand naphthalene series; and n is an integer between 4 and 40.
- n is an integer between 4 and 40.
- a photographic material comprising a base and a gelatino silver halide emulsion layer containing as a sensitizer therefor, a water soluble heterocyclic polyoxyalkylene compound of the following formula:
- A is a member selected from the group consisting of oxygen and sulfur; R and R are alkylene groups containing from 2 to 3 carbon atoms; X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino, vinylene; and Z represents the atoms necessary to complete an aromatic ring system of the benzene and naphthalene series; and n is an integer between 4 and 40.
- a photographic material comprising a base and a light-sensitive silver halide emulsion layer containing as a sensitizer therefor, a compound of the following formula:
- n is an integer between 4 and 40.
- a photographic material comprising a base and a light-sensitive silver halide emulsion layer containing as a sensitizer therefor, a compound of the following formula:
- n is an integer between 4 and 40.
- A is a member selected from the group consisting of oxygen and sulfur
- R and R are alltylene groups containing from 2 to 3 carbon atoms
- X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino and vinylene
- Z represents the atoms necessary to complete an aromatic ring system of the benzene and naphthalene series
- n is an integer between 4 and 40.
- n is an integer between 4 and 40.
- n is an integer between 4 and 40.
- A is a member selected from the group consisting of oxygen and sulfur; R and R are alkylene groups containing from 2 to 3 carbon atoms; X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino and vinylene; Z represents the 8 atoms necessary to complete an aromatic ring system of the benzene and naphthalene series; and n is an integer between 4 and 4O.
- a photographic developer solution comprising a silver halide developing agent, an alkali, an anti-oxidant, an antifoggant, and containing as a speed increasing agent a compound of the following formula:
- n is an integer between 4 and 40.
- a photographic developer solution comprising a silver halide developing agent, an alkali, an anti-oxidant, an antifoggant, and containing as a speed increasing agent a compound of the following formula:
- n is an integer between 4 and 40.
- a photographic developer solution comprising a silver halide developing agent, an alkali, an anti-oxidant, an 'antifoggant, and containing as a speed increasing agent a compound of the following formula:
- n is an integer between 4 and 40.
- a photographic material comprising a base having a layer of a light-sensitive silver halide emulsion thereon, said silver halide layer being in contiguous contact with another layer comprising a colloidal carrier and a watersoluble heterocyclic polyoxy-alkylene compound selected from the group consisting of those having the following general formula:
- A is a member selected from the group consisting of oxygen and sulfur; R and R are alkylene groups containing from 2 to 3 carbon atoms; X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino and vinylene; Z represents the atoms necessary to complete an aromatic ring system of the benzene and naphthalene series and n is an integer between 4 and 40.
- a photographic material comprising a base having a layer of a light-sensitive silver halide emulsion thereon, said silver halide being in contiguous contact with another layer comprising a colloidal carrier and a cornpou-nd of the following formula:
- n is an integer between 4 and 40.
- a photographic material comprising a base having a layer of a light-sensitive silver halide emulsion thereon, said silver halide being in contiguous contact with another layer comprising a colloidal carrier and a compound of the following formula:
- n is an integer between 4 and 40.
- a photographic material comprising a base having a layer of a light-sensitive silver halide emulsion thereon, said silver halide being in contiguous contact with another layer comprising a colloidal carrier and a compound of the following formula:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
trite ees att 3,046,130 PHOTOGRAPHIC MATERIALS CONTAINING A CHEMICAL SENSITIZER Fritz Dersch and Millet R. De Angelus, Binghamton, N.Y., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed May 12, 1960, Ser. No. 28,525 19 Claims. (Cl. 96-66) This invention relates to photographic materials. More particularly, this invention relates to photographic materials sensitized by means of water soluble heterocyclic compotmds which are substituted by a polyoxyalkylene chain.
It is well known that polyalkylene oxides such as polyoxyethylene and polyoxypropylene increase the speed of silver halide emulsions. It has also been observed that condensation products of alkylene oxides with amines, carboxylic acids, alcohols, amides or phenols (made according to U.S. Patents 1,970,578 and 2,213,- 477) and dicyclohexylol-dialkyl methane (see U.S. Patent 2,240,472) have been used as sensitizers. The polyalkylene oxides or the alkylene oxide condensation products should have a molecular weight of at least 300 and preferably 1,500 to 4,000 or more.
The use of the polyalkylene oxides or alkylene oxide condensation products as sensitizers is limited because of their tendency to increase the formation of fog during storage of the photographic film, especially storage at elevated temperature and high humidity. The use of conventioual antifoggants is not sufficient to satisfactorily eliminate or minimize fog formation in a film coated with an emulsion containing such products as sensitizers. Special antifoggants had to be found for use with such emulsions, and, in this connection, reference is made to U.S. Patents 2,704,716, 2,716,062 and 2,728,666.
It is an object of this invention to provide a novel seusitizer for use with a photographic emulsion or With a photographic developer to greatly increase the speed of the emulsion Without materially increasing the fogging tendency thereof, any tendency to fog being eliminated or minimized by the use of conventional autifoggants.
A further object of this invention is to provide a photographic film comprising a layer containing a water-soluble polyoxyalkylene derivative of a hydroXyor mercaptosubstituted azole in which the polyoxyalkylene chain replaces the hydrogen atom of the mercapto group.
Other objects and advantages of this invention Will appear to those skilled in the art from the detailed description thereof given below.
We have now discovered that Water-soluble oxyalkylene and polyoxyalkylene derivatives of Z-mercapto or 2-hydroxy-substituted azoles, namely, condensation products of alkylene oxide, e.g., ethylene oxide or propylene oxide, epichlorhydrine, trimethylene chlorhydriue or glycerol oz-chlorhydrine with a Z-hydroxyor Z-mercapto-substituted azole, e.g., benzothiazole, benzoxazole, benzimidazole or quinoline, have a remarkable speed increasing effect on silver halide emulsions. Surprisingly, these reaction products, unlike the heretofore used polyoxyalkylcues, do not have the objectionable tendency of increasing the fog of photographic films during storage especially under conditions of high temperature and high humidity.-
The fogging of photographic film having a coating of a silver halide emulsion and containing the novel sensitizer of our invention may, therefore, be controlled by the use of the conventional antifoggants and stabilizer used in the photographic art; and the use of a special type of antifoggant to prevent fogging of an emulsion containing conventional polyoxyalkylenes such as those disclosed in U.S. Patents 2,704,716, 2,716,062 and 2,728,666 becomes unnecessary.
. The polyoxyalkylene substituted heterocyclic compounds contemplated for use herein have the following general formula:
2-polyoxyethyleneoxybenzothiazole S 2-polyoxyethyleuemercaptobeuzothiarzole 2-polyoxyethylenemercaptoquinoliue NH 2-polyoxyethyleuepropyleneoxyrnercaptobeuzimidazole These heterocyclic polyoxyalkylene compounds are produced by introducing hydroxy aliphatic ether radlcals into 2hydroxyor Z-mercapto-substituted azoles according to the procedure described in United States Patent act . a t The above described heterocyclic compounds are condensed with hydroxy compounds such as ethylene oxide,
propylene oxide, epichlorhydrine, trimethylene chlorhydrine, glycerol a-chlorhydrine, glycol, glycerine, polyglycerine and the like. In some instances, two or more of these compounds are reacted consecutively with the mercaptoor hydroxy-substituted azole. Alkaline reacting compounds such as sodium or potassium hydroxide or heavy metal salts such as nickel sulfate serve as catalyzing agents.
The increase of effective sensitivity of photographic silver halide emulsions with the polyoxyalkylene derivatives of the Z-mercaptoor 2hydroxy-substituted heterocyclics can be obtained in a number of ways. They may be added to an undercoating, to a middle coating, to an overcoating or to a surface coating prior to the coating operation. If desired, they may be added during the actual preparation of the emulsion, either before or after washing of the emulsion.
The speed and sensitivity increasing agents of our invention may be used in various types of photographic emulsions; e.g., nonsensitized emulsions, orthochromatic,
' panchromatic, and X-ray emulsions. 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 a sensitive element, such as silver bromide, silver iodide, silver chloride or mixed silver halides. These hydroxy-substituted ether or thioether derivatives of heterocyclic compounds may be used in emulsions intended for color photography, e.g., emulsions containing color-forming components. The carrier in the photographic emulsion may be gelatin or other colloids such as collodion, albumen, cellulose derivatives, polyvinyl alcohol or synthetic resins. The emulsion containing our novel sensitizer may be coated on any conventional base, such as paper, glass, cellulose ester such as cellulose acetate, cellulose ethers and others.
The amounts of sensitivity increasing agents used per kilogram of emulsion range from 15 to 500 milligrams per kilogram of liquid emulsion. When expressed in terms of silver halide, the amounts of sensitivity increas ing agents range from 25 to 500 milligrams per mole of silver halide.
The sensitivity increasing agents of our invention can also be added to pre-bath solutions or to standard developer solutions. These developer solutions contain, in addition to the speed increasing agent, a developing agent such as metol, hydroquinone l-phenyl 3 pyrazolidone (phenidone); an alkali such as sodium or potassium carbonate; a preservative or anti-oxidant such as sodium sulfite; and an antifoggant such as potassium bromide. The amounts of speed increasing agents used range from 0.3 to 6.0 grams per liter of developer solution.
The following specific examples are given of the manner of producing and using the sensitizers of our invention. It is to be understood, however, that these examples are given by Way of illustration and not by way of limitation.
Example I s i G-S-QHzCI-Ia-(CHiCH9O) 1-I \NH A silver halide emulsion in gealtin containing 4 percent silver iodide and 96 percent silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. It was then readied for coating on film base, that is, melted at 40 C.; and the necessary coating finals were added, such as sensitizing dyes, stabilizers and hardeners. A percent aqueous solution of the reaction product of Z-mercaptobenzimidazole and 6 moles of ethylene oxide was prepare, and 10 cc. of this solution were added to a sample of the above described also Grams Meto-l (p-inethylaminophenol sulfate) 1.5 Sodium sulfite, anhydrous 45.0 Sodium bisulfite 1.0 Hydroquinone 3.0 Sodium carbonate, monohydrated 6.8 Potassium bromide .8
Water to make 1.0 liter.
The developed films were short-stopped, fixed and washed in the conventional manner. The results ob tained were as follows:
The ethylene oxide derivative of Z-mercaptobenzimidazole which served as a sensitizer was prepared as follows: 50 grams of Z-mercaptobenzimidazole was mixed with 0.5 gram of potassium hydroxide which had been dissolved in a minimum amount oi: water; the mass was heated to C.; ethylene oxide was passed through until 6 moles of ethylene oxide had been taken up.
The procedure was the same as in Example I excepting that there was used the reaction product of Z-mercaptobenzimidazole and trimethylene chlorhydrine which was then condensed with 8 moles of ethylene oxide. The results were similar to those obtained in Example I.
This addition product was prepared as described in Example VI of United States Patent 2,642,430.
Example III a tea Pg The procedure was the same as in Example I excepe ing that the reaction product of 2-hydroxybenzothiazole and 4 moles of propylene oxide iodide was used. The results were similar to those obtained in Example I.
The compound was prepared by heating under reflux 1 mole of 2-hydroxybenzothiazole and 1 mole of propylene oxide for 1 hour using a small amount of potassium hydroxide. Additional increments of propylene oxide were added while heating and refluxing continued until a total of 4 moles of propylene oxide had been consumed.
Example V One kilo of a silver halide emulsion in gelatin containing 4 percent silver iodide and 96 percent silver bromide was coated on film base in a manner known to the art. After the coating was performed, an aqueous gelatin solution containing 20 grams of gelatin per liter and 20 milligrams of the polyoxyethylene derivative of 2-mercaptobenzimidazole of Example I was coated thereon as an anti-abrasion layer. After drying, film samples were exposed and processed as described in Example I. The samples described exhibited a relative speed of 150 with a fog of .22 as compared with a type coating of the same emulsion having an anti-abrasion layer similar to that described above, but lacking the speed increasing additive and having a speed of 100 and a fog of .20.
Example Vl Several samples of a conventional photographic film were exposed in a type II-B sensitometer and then divided into two groups. One group of samples was developed for twelve minutes at 68 F. in a standard metolhydroquinone developer as described in Example I. The other group of samples was developed for the same length of time and at the same temperature as the first group in a metol-hydroquinone developer which had been prepared by adding to 1 liter of the developer described in Example I, 2 grams of the reaction product of ethylene oxide and Z-mercaptobenzimidazole. It was found that the samples developed in the standard developer had a relative speed of 100 whereas the samples developed in the developer containing the novel sensitivity increasing agent of our invention showed a relative speed of 175 without an increase in fog. Modifications of the invention will occur to persons skilled in the art. Thus, it is evident that in lieu of the ethylene oxide addition products of the examples, any of the addition products mentioned above may be em ployed in our invention. We, therefore, do not intend to be limited in the patent granted except as necessitated by the appended claims.
We claim: 7
1. A light-sensitive silver halide emulsion containing as a sensitizer therefor, a water soluble heterocyclic polyoxyalkylene compound selected from the group consisting of those having the following general formula:
wherein A is a member selected from the group consisting of oxygen and sulfur; R and R are alkylene groups containing from 2 to 3 carbon atoms; X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino and vinylene; Z represents the atoms necessary to complete an aromatic ring system of the benzeneand naphthalene series; and n is an integer between 4 and 40.
2. A light-sensitive silver halide emulsion containing as a sensitizer therefor, a compound of the following formula:
\I/ SCH2CHzO(CHzCHz0) H wherein n is an integer between 4 and 40.
4. A photographic material comprising a base and a gelatino silver halide emulsion layer containing as a sensitizer therefor, a water soluble heterocyclic polyoxyalkylene compound of the following formula:
wherein A is a member selected from the group consisting of oxygen and sulfur; R and R are alkylene groups containing from 2 to 3 carbon atoms; X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino, vinylene; and Z represents the atoms necessary to complete an aromatic ring system of the benzene and naphthalene series; and n is an integer between 4 and 40.
5. A photographic material comprising a base and a light-sensitive silver halide emulsion layer containing as a sensitizer therefor, a compound of the following formula:
wherein n is an integer between 4 and 40.
6. A photographic material comprising a base and a light-sensitive silver halide emulsion layer containing as a sensitizer therefor, a compound of the following formula:
wherein n is an integer between 4 and 40.
8. The process of increasing the sensitivity of a lightsensitive silver halide material comprising a base having a light-sensitive silver halide emulsion thereon which spaeaso z: o-A-rnO-ononon wherein A is a member selected from the group consisting of oxygen and sulfur; R and R are alltylene groups containing from 2 to 3 carbon atoms; X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino and vinylene; Z represents the atoms necessary to complete an aromatic ring system of the benzene and naphthalene series; and n is an integer between 4 and 40.
9. The process of increasing the sensitivity of a lightsensitive silver halide material comprising a base having a light-sensitive silver halide emulsion thereon, whicn comprises exposing said emulsion and developing the same in the presence of a compound having the following formula:
GSCH2CH2O(OHzOI-IZO)HH wherein n is an integer between 4 and 40.
10. The process of increasing the sensitivity of a lightsensitive silver halide material comprising a base having a light-sensitive silver halide emulsion thereon, which comprises exposing said emulsion and developing the same in the presence of a compound having the following formula:
\I/S-CI{QCIIZO-(CHZCHZO)X1H wherein n is an integer between 4 and 40.
ll. The process of increasing the sensitivity of a lightsensitive silver halide material comprising a base having a light-sensitive silver halide emulsion thereon, which comprises exposing said emulsion and developing the same in the presence of a compound having the following formula:
wherein A is a member selected from the group consisting of oxygen and sulfur; R and R are alkylene groups containing from 2 to 3 carbon atoms; X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino and vinylene; Z represents the 8 atoms necessary to complete an aromatic ring system of the benzene and naphthalene series; and n is an integer between 4 and 4O.
13. A photographic developer solution comprising a silver halide developing agent, an alkali, an anti-oxidant, an antifoggant, and containing as a speed increasing agent a compound of the following formula:
wherein n is an integer between 4 and 40.
14. A photographic developer solution comprising a silver halide developing agent, an alkali, an anti-oxidant, an antifoggant, and containing as a speed increasing agent a compound of the following formula:
wherein n is an integer between 4 and 40.
15. A photographic developer solution comprising a silver halide developing agent, an alkali, an anti-oxidant, an 'antifoggant, and containing as a speed increasing agent a compound of the following formula:
wherein n is an integer between 4 and 40.
16. A photographic material comprising a base having a layer of a light-sensitive silver halide emulsion thereon, said silver halide layer being in contiguous contact with another layer comprising a colloidal carrier and a watersoluble heterocyclic polyoxy-alkylene compound selected from the group consisting of those having the following general formula:
wherein A is a member selected from the group consisting of oxygen and sulfur; R and R are alkylene groups containing from 2 to 3 carbon atoms; X represents the atoms necessary to complete a heterocyclic mononuclear ring and is a member selected from the group consisting of oxygen, sulfur, imino and vinylene; Z represents the atoms necessary to complete an aromatic ring system of the benzene and naphthalene series and n is an integer between 4 and 40.
17. A photographic material comprising a base having a layer of a light-sensitive silver halide emulsion thereon, said silver halide being in contiguous contact with another layer comprising a colloidal carrier and a cornpou-nd of the following formula:
wherein n is an integer between 4 and 40.
18. A photographic material comprising a base having a layer of a light-sensitive silver halide emulsion thereon, said silver halide being in contiguous contact with another layer comprising a colloidal carrier and a compound of the following formula:
wherein n is an integer between 4 and 40.
19. A photographic material comprising a base having a layer of a light-sensitive silver halide emulsion thereon, said silver halide being in contiguous contact with another layer comprising a colloidal carrier and a compound of the following formula:
References Cited in the file of this patent UNITED STATES PATENTS 2,944,902 Carroll et al July 12, 1960
Claims (1)
12. A PHOTOGRAPHIC DEVELOPER SOLUTION COMPRISING A SILVER HALIDE DEVELOPING AGENT, AN ALKALI, AN ANTI-OXIDANT AND AN ANTIFOGGANT CONTAINING AS A SPEED INCREASING AGENT A WATER-SOLUBLE HETEROCYCLIC POLYOXYALKYLENE COMPOUND SELECTED FROM THE GROUP CONSISTING OF THOSE HAVING THE FOLLOWING GENERAL FORMULA:
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28525A US3046130A (en) | 1960-05-12 | 1960-05-12 | Photographic materials containing a chemical sensitizer |
DEG32190A DE1159267B (en) | 1960-05-12 | 1961-05-02 | Methods for increasing the sensitivity of photographic materials, light-sensitive materials, halide silver emulsions and developers therefor |
FR861295A FR1294983A (en) | 1960-05-12 | 1961-05-09 | Photographic materials containing a chemical sensitizer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US28525A US3046130A (en) | 1960-05-12 | 1960-05-12 | Photographic materials containing a chemical sensitizer |
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US3046130A true US3046130A (en) | 1962-07-24 |
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ID=21843932
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US28525A Expired - Lifetime US3046130A (en) | 1960-05-12 | 1960-05-12 | Photographic materials containing a chemical sensitizer |
Country Status (3)
Country | Link |
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US (1) | US3046130A (en) |
DE (1) | DE1159267B (en) |
FR (1) | FR1294983A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3155514A (en) * | 1961-12-08 | 1964-11-03 | Du Pont | Photographic compositions and elements |
US3155517A (en) * | 1962-11-08 | 1964-11-03 | Du Pont | Photographic compositions and elements |
US3630745A (en) * | 1969-10-08 | 1971-12-28 | Eastman Kodak Co | THIAZOLO {8 5,4-c{9 ISOQUINOLINE AND THIAZOLO {8 4,5-c{9 IOSQUINOLINE AND DERIVATIVES AS ANTIFOGGANTS FOR PHOTOGRAPHIC LAYERS |
US3940271A (en) * | 1973-02-02 | 1976-02-24 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
US4116697A (en) * | 1976-12-17 | 1978-09-26 | E. I. Du Pont De Nemours And Company | Sulfur-substituted isothioureas in silver halide emulsions |
FR2732018A1 (en) * | 1995-03-20 | 1996-09-27 | Bp Chemicals Snc | New ethoxylated mercapto-2-benzimidazole useful as corrosion inhibiting agent |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2944902A (en) * | 1956-07-30 | 1960-07-12 | Eastman Kodak Co | Sensitization of photographic emulsions with ionic polyalkylene oxide salts |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2728666A (en) * | 1952-11-08 | 1955-12-27 | Eastman Kodak Co | Stabilization of emulsions sensitized with alkylene oxide polymers |
BE530063A (en) * | 1953-07-01 | |||
US2704716A (en) * | 1954-06-17 | 1955-03-22 | Eastman Kodak Co | Melonate and cyamelurate stabilizers for photographic emulsions sensitized with alkylene oxide polymers |
BE553031A (en) * | 1955-12-01 |
-
1960
- 1960-05-12 US US28525A patent/US3046130A/en not_active Expired - Lifetime
-
1961
- 1961-05-02 DE DEG32190A patent/DE1159267B/en active Pending
- 1961-05-09 FR FR861295A patent/FR1294983A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2944902A (en) * | 1956-07-30 | 1960-07-12 | Eastman Kodak Co | Sensitization of photographic emulsions with ionic polyalkylene oxide salts |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3155514A (en) * | 1961-12-08 | 1964-11-03 | Du Pont | Photographic compositions and elements |
US3155507A (en) * | 1961-12-08 | 1964-11-03 | Du Pont | Photographic processes |
US3155516A (en) * | 1961-12-08 | 1964-11-03 | Du Pont | Photographic products |
US3155515A (en) * | 1961-12-08 | 1964-11-03 | Du Pont | Photographic products |
US3155517A (en) * | 1962-11-08 | 1964-11-03 | Du Pont | Photographic compositions and elements |
US3630745A (en) * | 1969-10-08 | 1971-12-28 | Eastman Kodak Co | THIAZOLO {8 5,4-c{9 ISOQUINOLINE AND THIAZOLO {8 4,5-c{9 IOSQUINOLINE AND DERIVATIVES AS ANTIFOGGANTS FOR PHOTOGRAPHIC LAYERS |
US3940271A (en) * | 1973-02-02 | 1976-02-24 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
US4116697A (en) * | 1976-12-17 | 1978-09-26 | E. I. Du Pont De Nemours And Company | Sulfur-substituted isothioureas in silver halide emulsions |
FR2732018A1 (en) * | 1995-03-20 | 1996-09-27 | Bp Chemicals Snc | New ethoxylated mercapto-2-benzimidazole useful as corrosion inhibiting agent |
Also Published As
Publication number | Publication date |
---|---|
DE1159267B (en) | 1963-12-12 |
FR1294983A (en) | 1962-06-01 |
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