US3909268A - Tetrazolium C-oxy-betaine compounds as antifog agents for silver halide photographic emulsions - Google Patents
Tetrazolium C-oxy-betaine compounds as antifog agents for silver halide photographic emulsions Download PDFInfo
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- US3909268A US3909268A US465185A US46518574A US3909268A US 3909268 A US3909268 A US 3909268A US 465185 A US465185 A US 465185A US 46518574 A US46518574 A US 46518574A US 3909268 A US3909268 A US 3909268A
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- United States
- Prior art keywords
- oxy
- tetrazolium
- betaine
- emulsion
- compound
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- Expired - Lifetime
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- 239000000839 emulsion Substances 0.000 title claims abstract description 71
- -1 silver halide Chemical class 0.000 title claims abstract description 40
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 39
- 239000004332 silver Substances 0.000 title claims abstract description 39
- 125000003831 tetrazolyl group Chemical group 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 title abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 229960003237 betaine Drugs 0.000 claims description 42
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 33
- 230000002401 inhibitory effect Effects 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 11
- 238000011161 development Methods 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 67
- 239000010410 layer Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 229960003116 amyl nitrite Drugs 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 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
- 239000000654 additive Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- QAXZWHGWYSJAEI-UHFFFAOYSA-N n,n-dimethylformamide;ethanol Chemical compound CCO.CN(C)C=O QAXZWHGWYSJAEI-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 231100000489 sensitizer Toxicity 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- VOVLASAYEAYVHD-UHFFFAOYSA-N benzene-1,4-diol;1-phenylpyrazolidin-3-one Chemical compound OC1=CC=C(O)C=C1.N1C(=O)CCN1C1=CC=CC=C1 VOVLASAYEAYVHD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- QFXBXCAZEVOLGQ-UHFFFAOYSA-N n'-amino-n-nitroiminomethanimidamide Chemical compound NN=CN=N[N+]([O-])=O QFXBXCAZEVOLGQ-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- 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
- tetrazolium C-oxy-betaine compounds are very effective agents both used in a photographic element reactively associated with the silver emulsion and in a processing bath adapted for use prior to or during development of emulsion layers. They surprisingly show a very good antifogging effect with a low desensitization effect. They can also be used in combination with high temperature processing baths containing or not aldehydes as hardening agents.
- the compounds useful according to the present invention are preferably those represented by the following formula:
- an aryl group is a phenyl group or a naphthyl group.
- the phenyl or naphthyl group will not contain more than a total of twelve 12) carbon atoms therein.
- Substituents, if any, are preferred from halogen, alkyl, alkoxy, perfluoroalkyl, haloalkyl and acyl. The substituents therefore preferably have no more than six (6) carbon atoms when attached to a phenyl ring and no more than two (2) carbon atoms when attached to a naphthyl group.
- the phenyl or naphthyl ring may contain more than one of any substituent.
- the molecular weight of the' aryl group is preferably below 300 and more preferably below 200.
- the invention in one aspect relates to a silver halide emulsion having contacted therewith a tet-.
- the invention in another aspect relates to a silver halide photographic element having a silver halide. emulsion layer and having a tetrazolium C-oxy-betaine compound in reactive association therewith (eg in the emulsion layer or a layer adjacent the emulsion layer).
- the invention in a further aspect relates to a method for inhibiting fog in a silver halide photographic emulsion which comprises contacting said emulsion with a tetrazolium C-oxybetaine compound.
- the invention further relates to an improved method for processing an exposed silver halide element, which includes treating said element with a series of photographic treatment solutions including a development solution, the improvement comprising contacting said element during said processing with a tetrazolium C-oxy-betaine compound, said compound being contained in said development solution and/or in a pre-development treatment solution.
- the invention relates to a processing solution adapted for use prior to or during development of a silver photographic element, containing or not an aldehyde as hardener, containing a fog inhibiting amount of a tetrazolium C-oxy-betaine compound.
- Tetrazolium C-oxy-betaine compounds as a class have been found useful as fog inhibiting agents for silver halide emulsions when reactively associated therewith. It has been found that substituents attached to nitrogen atoms do not substantially vary the capacity of the compounds to inhibit fog.
- tetrazolium C-oxy-betaine compounds of the of the corresponding c-nitro-formazanes, according to present invention have been prepared upon oxidation what described by A. W. Nineham, Chem. Review 55 (1955 406 and by F. Bamberger, R. Padova, E. Ormerod, Ann. Chem. 446 (1926), 260-307. Different preparation methods have been followed corresponding to different oxidizing agents; that is to say that the hereinafter illustrated methods respectively correspond to the oxidizing agents: amylnitrite, N-bromosuccinimide, lead acetate, sodium hypochlorite.
- the C-nitroformazanes have been prepared upon reaction between an aryldiazolium chloride, obtained in a conventional way, and an alkaline nitromethane solution at a temperature ranging from -1 5 to C, in aqueous environment and in the presence of sodium acetate according to what described by E. Bamberger, R. Padova, E. Ormerod, Ann. Chem. 446 (1926) 260-307 and by D.
- Example No. 7 Samples of said emulsions were then exposed under a tungsten lamp and developed for 5' at 20C with a de- (M 5 Moles of 1,5 (3,4 dimethyl) phenyl 3 veloper having the following composition: nitroformazane were dissolved in 600 ml of chloro form. 0.11 moles of N-bromo-succinimide were then Memo] 2 2 added thereto slowly and the whole was heated up to Hydmquinone 2 60-70C. The red solution underwent a discoloration. Sodiurn Sulfie aflhydmus 72 g It was then cooled, poured into 2 l.
- M 5 Moles of 1,5 (3,4 dimethyl) phenyl 3 veloper having the following composition: nitroformazane were dissolved in 600 ml of chloro form. 0.11 moles of N-bromo-succinimide were then Memo] 2 2 added thereto slowly and the whole was heated up to Hydmquino
- This table shows the sensitometric results respectively obtained with a fresh film and with a filni incubated for 15 h at 72C and 30% R.H.
- the sensitivity is expressed in log E.
- the figures shown therein are sensitivity differences (A sens.) measured with respect to the reference emulsion.
- the compounds can he introduced into the bath by using a solvent as in the case of introduction into the emulsion. or not.
- the silver halide photographic emulsions of the present invention are silver chloride, silver bromide and silver iodide emulsions and mixtures thereof such as for example silver bromoiodide and silver chlorobromide iodide.
- Such emulsions may include synthetic polymeric gelatin substitutes or additives, such as dextrane, polyvinyl alcohol, polyvinyl pyrrolidone, partially hydrolized polyvinyl acetate, polyethylacrylate, polymethylmethacrylate, polyamides, etc.
- the emulsions of the invention may be chemically sensitized with naturally active gelatine, by addition of chemical sensitizers Table 4 Fresh incubated Compound Solvent mM/M AgX A Sensitivity Fog A Sensitivity Fog 0.67 0.64 (a) DMF 0.05 0.29 0.46 0.34 0.36 (a) DMF 0.25 0.24 0.57 0.15 0.42 (a) DMF 0.10 O.17 0.59 0.l9 0.48 (b) DMF 0.05 0.05 0.57 0.09 0.55 Ex. 1 DMF 0.5 0.03 0.32 0.00 0.30 Ex. 2 DMF 0.5 0.l2 0.43 0.00 0.45 Ex. 3 DMF 0.5 0.03 0.36 0.00 0.39 Ex. 4 DMF 0.5 0.08 0.43 0.04 0.42 Ex.
- Sensitization may be effected by the addition of noble metals, such as gold salts.
- Spectral sensi tizers may be employed in emulsions of the invention, such as cyanine and merocyanine dyes.
- the emulsions of the invention may include such additives as color couplers, filtering dyes, surfactants, hardeners, stabilizers, additional fog restrainers, plasticizers, antioxidizing agents, developing accelerators, etc.
- a photographic element comprises one support such as polyester, cellulose acetate, and the like and at least one layer including a silver halide emulsion layer of the above described type coated thereon.
- Such element can additionally contain other layers, that is, protective layers, interlayers, antihalo layers, filter layers, etc.
- the tetrazolium C-oxy-betaine compounds of the invention may be conveniently introduced in the form of solutions into emulsions or any other coating composition during preparation thereof. Although it is generally preferred to incorporate the tetrazolium C-oxybetaine compounds of the invention directly into emulsion layers, these compounds may also be incorporated into layers adjacent the emulsion layers so that the silver halide emulsions are again in reactive association therewith.
- the tetrazolium C-oxy-betaine compounds are preferably introduced into photographic elements reactively associated with the silver halide emulsions in amounts ranging from about 0.05 to 3 mM/M of silver halide and most preferably from 0.1 to 2 mM/M of silver halide.
- the processing baths of the present invention may be photographic pre-baths, such as those known to the art to be useful prior to treatment of a silver halide photographic element with a developing solution
- Predevelopment baths are usually (but not necessarily) acidic and may contain hardeners such as aldehydes and the like.
- the tetrazolium C-oxy-betaine compounds of the invention may, of course, also be employed in developing baths.
- Such baths are normally alkaline and include one or more silver halide photographic developing agents such as hydroquinone, metol, metolhydroquinone, phenidone, hydroquinonephenidone, and various p-phenylene diamine materials, the latter being useful in color development processes.
- the processing baths of the invention (prebaths and developer baths) preferably include from about 1 to mM/liter of solution and most preferably from 2 to 5 mM/liter of solution.
- a silver halide photographic emulsion having in reactive contact therewith at least a fog-inhibiting amount of a tetrazolium C-oxy-betaine compound.
- a silver halide photographic emulsion having in reactive contact therewith at least a fog-inhibiting amount of a tetrazolium C-oxy-betaine compound corresponding to the formula 3.
- said antifogging compound is 2 ,3-di-phenyl-5-oxy-tetrazolium betaine.
- antifogging compound is 2,3-di(4-chloro-phenyl)5-oxytetrazolium betaine.
- antifogging compound is 2,3-di-(3-trifluoromethyl-phenyll5-oxytetrazolium betaine.
- antifogging compound is 2,3-di-(3-chloro-4-methyl-phenyl)S-oxytetrazolium betaine.
- antifogging compound is 2,3-di-(3,4-di-methyl-phenyll5-oxytetrazolium betaine.
- antifogging compound is 2,3-di-(2-acetyl-5-chloro-phenyl)5-oxytetrazolium betaine.
- antifogging compound is 2,3-di-(2-chloro-phenyll5-oxytetrazolium betaine.
- said antifogging compound is 2,3-di-( 3 ,4-di-chloro-phenyb5oxytetrazolium betaine.
- a silver halide photographic element having a silver halide emulsion layer and a fog-inhibiting amount of a tetrazolium C-oxy-betaine compound in reactive association therewith.
- a silver halide photographic element having a silver halide emulsion layer and a fog-inhibiting amount of a tetrazolium C-oxy-betaine of formulas respectively corresponding to those referred to in claims 2 in reactive association therewith.
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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)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT49830/73A IT984942B (it) | 1973-05-07 | 1973-05-07 | C ossi betaine di tetrazolio come agenti antivelo per emulsioni foto grafiche agli alogenuri d argento |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3909268A true US3909268A (en) | 1975-09-30 |
Family
ID=11271660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US465185A Expired - Lifetime US3909268A (en) | 1973-05-07 | 1974-04-29 | Tetrazolium C-oxy-betaine compounds as antifog agents for silver halide photographic emulsions |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US3909268A (fr) |
| JP (1) | JPS5855496B2 (fr) |
| AR (1) | AR201583A1 (fr) |
| BE (1) | BE814663A (fr) |
| CA (1) | CA1030002A (fr) |
| DE (1) | DE2422069A1 (fr) |
| FR (1) | FR2229080B1 (fr) |
| GB (1) | GB1466740A (fr) |
| IT (1) | IT984942B (fr) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2734336A1 (de) * | 1976-07-31 | 1978-02-02 | Konishiroku Photo Ind | Lichtempfindliches photographisches silberhalogenidaufzeichnungsmaterial |
| DE2734335A1 (de) * | 1976-07-31 | 1978-02-02 | Konishiroku Photo Ind | Lichtempfindliches photographisches silberhalogenidaufzeichnungsmaterial |
| US4175966A (en) * | 1975-08-02 | 1979-11-27 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof |
| US4192682A (en) * | 1977-01-26 | 1980-03-11 | Konishiroku Photo Industry Co., Ltd. | Process of forming a high-contrast silver image |
| US4210715A (en) * | 1975-08-02 | 1980-07-01 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material and method of processing thereof |
| US4211835A (en) * | 1977-01-27 | 1980-07-08 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material and method of processing the same |
| US4221864A (en) * | 1977-02-01 | 1980-09-09 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic materials |
| US4233400A (en) * | 1975-08-02 | 1980-11-11 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material containing tetrazolium compounds |
| US4268620A (en) * | 1977-01-31 | 1981-05-19 | Konishiroku Photo Industry Co., Ltd. | Method of processing of light-sensitive silver halide photographic material |
| US4376903A (en) * | 1975-12-23 | 1983-03-15 | Micro Technology Laboratory Co., Ltd. | Direct current dynamo electric machine |
| US4416980A (en) * | 1977-01-28 | 1983-11-22 | Konishiroku Photo Industry Co., Ltd. | High-contrast light-sensitive silver halide photographic material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4265794A (en) | 1976-01-07 | 1981-05-05 | Ford Motor Company | Moldable mixture of sacrificial binder and sinterable particulate solids |
| JPS61296348A (ja) * | 1985-06-25 | 1986-12-27 | Konishiroku Photo Ind Co Ltd | ハロゲン化銀写真感光材料 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3023103A (en) * | 1960-08-02 | 1962-02-27 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3420664A (en) * | 1966-01-03 | 1969-01-07 | Gaf Corp | Dehydrodithizone and mercaptotetrazolium salts as silver halide photographic antifoggants and stabilizers |
-
1973
- 1973-05-07 IT IT49830/73A patent/IT984942B/it active
-
1974
- 1974-04-29 US US465185A patent/US3909268A/en not_active Expired - Lifetime
- 1974-05-06 CA CA199,054A patent/CA1030002A/fr not_active Expired
- 1974-05-06 FR FR7415516A patent/FR2229080B1/fr not_active Expired
- 1974-05-06 GB GB1989374A patent/GB1466740A/en not_active Expired
- 1974-05-07 DE DE2422069A patent/DE2422069A1/de not_active Ceased
- 1974-05-07 JP JP49050638A patent/JPS5855496B2/ja not_active Expired
- 1974-05-07 AR AR253633A patent/AR201583A1/es active
- 1974-05-07 BE BE144019A patent/BE814663A/fr not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3023103A (en) * | 1960-08-02 | 1962-02-27 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsions |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4175966A (en) * | 1975-08-02 | 1979-11-27 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof |
| US4210715A (en) * | 1975-08-02 | 1980-07-01 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material and method of processing thereof |
| US4233400A (en) * | 1975-08-02 | 1980-11-11 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material containing tetrazolium compounds |
| US4376903A (en) * | 1975-12-23 | 1983-03-15 | Micro Technology Laboratory Co., Ltd. | Direct current dynamo electric machine |
| DE2734336A1 (de) * | 1976-07-31 | 1978-02-02 | Konishiroku Photo Ind | Lichtempfindliches photographisches silberhalogenidaufzeichnungsmaterial |
| DE2734335A1 (de) * | 1976-07-31 | 1978-02-02 | Konishiroku Photo Ind | Lichtempfindliches photographisches silberhalogenidaufzeichnungsmaterial |
| US4192682A (en) * | 1977-01-26 | 1980-03-11 | Konishiroku Photo Industry Co., Ltd. | Process of forming a high-contrast silver image |
| US4211835A (en) * | 1977-01-27 | 1980-07-08 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material and method of processing the same |
| US4416980A (en) * | 1977-01-28 | 1983-11-22 | Konishiroku Photo Industry Co., Ltd. | High-contrast light-sensitive silver halide photographic material |
| US4268620A (en) * | 1977-01-31 | 1981-05-19 | Konishiroku Photo Industry Co., Ltd. | Method of processing of light-sensitive silver halide photographic material |
| US4221864A (en) * | 1977-02-01 | 1980-09-09 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic materials |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5855496B2 (ja) | 1983-12-09 |
| DE2422069A1 (de) | 1974-12-05 |
| BE814663A (fr) | 1974-11-07 |
| JPS5032930A (fr) | 1975-03-29 |
| FR2229080A1 (fr) | 1974-12-06 |
| IT984942B (it) | 1974-11-20 |
| GB1466740A (en) | 1977-03-09 |
| FR2229080B1 (fr) | 1977-10-21 |
| CA1030002A (fr) | 1978-04-25 |
| AR201583A1 (es) | 1975-03-31 |
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