US3925086A - Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions - Google Patents
Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions Download PDFInfo
- Publication number
- US3925086A US3925086A US235011A US23501172A US3925086A US 3925086 A US3925086 A US 3925086A US 235011 A US235011 A US 235011A US 23501172 A US23501172 A US 23501172A US 3925086 A US3925086 A US 3925086A
- Authority
- US
- United States
- Prior art keywords
- emulsion
- azotetrazole
- azotriazole
- silver halide
- fog
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 85
- -1 silver halide Chemical class 0.000 title claims abstract description 35
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 33
- 239000004332 silver Substances 0.000 title claims abstract description 33
- WUPZAQSKRMYJNB-MDZDMXLPSA-N 1,1'-azobis-1,2,3-triazole Chemical compound N1=NC=CN1\N=N\N1N=NC=C1 WUPZAQSKRMYJNB-MDZDMXLPSA-N 0.000 title claims description 21
- JGZAFSFVZSXXCJ-ONEGZZNKSA-N (E)-bis(2H-tetrazol-5-yl)diazene Chemical compound N(=N\C1=NN=NN1)/C1=NN=NN1 JGZAFSFVZSXXCJ-ONEGZZNKSA-N 0.000 title claims description 18
- 229940090898 Desensitizer Drugs 0.000 title abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 230000002401 inhibitory effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 description 36
- 239000000243 solution Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000203 mixture Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- YGZZDQOCTFVBFC-UHFFFAOYSA-L disodium;1,5-dihydroxypentane-1,5-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C(O)CCCC(O)S([O-])(=O)=O YGZZDQOCTFVBFC-UHFFFAOYSA-L 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000837 restrainer Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 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
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 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 2
- 239000000654 additive Substances 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- RFDMWAAVQQFVFK-FOCLMDBBSA-N (e)-bis(1-phenyltetrazol-5-yl)diazene Chemical group C1=CC=CC=C1N1C(\N=N\C=2N(N=NN=2)C=2C=CC=CC=2)=NN=N1 RFDMWAAVQQFVFK-FOCLMDBBSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-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
- QAHJJQGHAWTUQU-UHFFFAOYSA-N 5-methyl-2h-triazol-4-amine Chemical compound CC1=NNN=C1N QAHJJQGHAWTUQU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 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
- VEKBRXKPWIDPTK-UHFFFAOYSA-N [Na+].[Cl+].Cl[O-].Cl[O-] Chemical compound [Na+].[Cl+].Cl[O-].Cl[O-] VEKBRXKPWIDPTK-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000326 densiometry Methods 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 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
- 229910052757 nitrogen Chemical group 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- WZWGGYFEOBVNLA-UHFFFAOYSA-N sodium;dihydrate Chemical compound O.O.[Na] WZWGGYFEOBVNLA-UHFFFAOYSA-N 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
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/14—Nitrogen atoms
-
- 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
- C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
-
- 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
- G03C1/33—Spot-preventing agents
-
- 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
- G03C1/36—Desensitisers
Definitions
- ABSTRACT Azotriazoles and azotetrazoles are effective antifogging agents, antistain agents and selective desensitizers for silver halide photographic emulsions, Such agents may be employed in reactive association with the emulsions, or in a processing bath prior to or during development of emulsion layersv 12 Claims, No Drawings AZOTRIAZOLE AND AZOTETRAZOLE ANTIFOG, ANTISTAIN AND SELECTIVE DESENSITIZERS FOR SILVER HALIDE EMULSIONS
- the present invention relates to the use of azotriazoles and azotetrazoles as anti-fog, anti-stain and/or selective desensitizers for silver halides photographic emulsions.
- azotriazole and azotetrazole compounds are capable of inhibiting fog when placed in contact with a silver halide emulsion (as by being placed in the emulsion, in a layer adjacent the emulsion, or by being placed in a processing bath which is employed prior to or during development of the emulsion). These compounds have also been found to inhibit stains in silver halide photographic emulsions, and, in larger quantities, to selectively desensitize silver halide emulsions.
- the present invention relates to a silver halide photographic emulsion having contacted therewith at least a fog-inhibiting amount of an azotriazole or an azotetrazole.
- the invention relates to a method for in hibiting fog in a silver halide photographic emulsion which comprises contacting the emulsion with an azotetrazole or an azotriazole.
- the invention relates to an aqueous processing solution for silver halide photographic emulsions adapted for use prior to or during development and containing from about 3 to about 6 milligrams of an azotriazole or an azotetrazole per liter of solution.
- azotriazoles and azotetrazoles of the present invention preferably correspond to the formula 2 z' I c N N c N l N wherein Z and Z independently represent atoms forming heterocyclic nuclei of the triazole or tetrazole series.
- sub stituents borne by the heterocyclic nuclei of the azotriazoles and azotetrazoles of the invention include hydrogen, alkyl (e.g., C,C alkyl), alkaline (e.g., C C and aryl (e.g., phenyl, naphthyl, including substituted aryl such as alkaryl having no more than 15 aliphatic carbon atoms, etc.).
- the azotriazoles and azotetrazoles of the present invention correspond to the formula wherein X is carbon or nitrogen, and each Y group independently represents a hydrogen atom, an alkyl group (e.g., C,C an alkaline group (e.g., C,C or an aryl group (e.g., phenyl, naphthyl, including substituted aryl such as alkaryl containing no more than 20 aliphatic carbon atoms), etc.
- an alkyl group e.g., C,C an alkaline group (e.g., C,C or an aryl group (e.g., phenyl, naphthyl, including substituted aryl such as alkaryl containing no more than 20 aliphatic carbon atoms), etc.
- the present invention permits a single class of fog restrainers to be used for many purposes.
- the triazoles and tetrazoles of the invention are useful both in photographic silver halide emulsions, (e.g., mixed into the emulsion layer or employed in a layer adjacent the emulsion layer) and in photographic processing baths which, for example, are employed either prior to development (as a pre-bath), in the developing bath itself, etc.
- the azotriazole and azotetrazole compounds of the invention are particularly desirable because they are generally readily soluble in common photographic solvents such as water, alcohol, and aqueous alkaline solutions such as developer solutions.
- This compound can be usefully introduced into a photographic emulsion or photographic bath in aqueous solutions of sodium carbonate or NaOH.
- This compound can be usefully introduced into an emulsion or photographic bath in solutions of sodium carbonate or NaOH.
- This compound can be usefully introduced into a photographic silver halide emulsion or into a photographic bath in ethanol of dimethylformamide solution.
- This compound can be usefully introduced into emulsions or photographic baths in ethanol solution.
- This compound can be usefully introduced into emulsions or photographic baths in ethanol solution.
- This compound can be usefully introduced into emul- Thls compound l be Introduced emul' sions or photographic baths in ethanol solution. 40 Slons or phowgraphlc baths m ethanol soluuon Analysis: Calculated Found Analysis: Calculated Found 5% 22.3% 23.3 c% 38.49 38.42 11% 4.06 4.21 N% 72.10 11.42 N% 56.89 56.28
- EXAMPLE 7 EXAMPLE 9 1,1'-diallyl-5,5-azotetrazole
- compound C suitable CH2 CH CH2 N a 5g solvents have been selected, and the solubility of these N L compounds at 20C in these solvents has been determined. The results are reported in the following table 1.
- EXAMPLE ll EXAMPLE I4 65 Photographic material similar to that of Example 10 A quantity of the developer of Example 10 was divided into two portions. To one portion was added 50 42M of the compound of Example 2. Samples of the photographic material of Example [0, exposed to light was exposed to the light from a tungsten lamp and divided into three samples. One sample was developed in a developer of the following formula:
- the second sample was identically developed except that the developer containing 200 p.M per liter of the compound of Example 2.
- EXAMPLE 16 To samples of a medium sensitivity, physically seasoned, washed and chemically sensitized silver bromoiodide emulsion containing 97.5 moles of bromide and 2.5 mole of iodide, were added various amounts of compounds of the present invention, of red mercury iodide (a known selective desensitizer), and of l-phenyl-S-mercaptotetrazole (labeled A).
- the resulting emulsions were then spread on cellulose triacetate supports, and samples of the corresponding materials were exposed to white light and to X-rays of various energy. The exposed samples were then developed for 3 minutes at 20C in the developer of Example 10.
- EXAMPLE 17 A cellulose triacetate support was thinly coated with gelatin containing powdered iron. Three samples of the resulting material, drawn at random, were each divided into four parts. On the first part a high sensitivity, silver bromo-iodide containing 98 moles of bromide and 2 mole of iodide were coated. On the other three parts of each sample, the same emulsion to which had been added respectively the compounds of Examples 1 and 2 and the 1-phenyl-S-mercapto-tetrazole (labeled A) were coated. On each element thus obtained a protective gelatin layer was coated. The resulting elements were kept 10 minutes in a cold state and were then developed 10 minutes at 20C in the developer of Example 10. The white and black points on each of the resulting elements were counted.
- the developed material was fixed in a bath of the following composition: 10
- the silver halide photographic emulsions of the pres- 30 ent 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,
- the emulsions of the invention may be chemically sensitized with naturally active gelatin, by addition of chemical sensitizers such as thiourea, allylthiourea, thiocyanates, thiosulfates, etc. Sensitization may be effected by the addition of noble metals, such as gold salts. Spectral sensitizers 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, oxidizing agents, developing accelerators, etc.
- the emulsions of the invention may be coated upon any convenient support such as polyester, cellulose acetate, and the like.
- 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 photographic emulsion with a developing solution.
- Predevelopment baths usually (but not necessarily) are acidic and may contain hardeners such as aldehydes and the like.
- the azotriazole and azotetrazole 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, metol-hydroquinone, phenidone, hydroquinonephenidone, and various p-phenylene diamine materials,
- processing baths of the invention preferably employ from 3 to about 60 milligrams of azotriazole or azotetrazole compound per liter of solution.
- a silver halide photographic emulsion having contacted therewith at least a fog-inhibiting amount of an azotriazole or an azotetrazole.
- anti-fogging agent is a 5,5'-azotetrazole-l,l '-disodium salt.
- a method for inhibiting fog in a silver halide photographic emulsion which comprises contacting said emulsion with an azotetrazole or an azotriazole.
- a method for inhibiting fog and stain in a silver halide emulsion which comprises contacting said emulsion with an azotriazole or an azotetrazole.
Abstract
Azotriazoles and azotetrazoles are effective anti-fogging agents, anti-stain agents and selective desensitizers for silver halide photographic emulsions. Such agents may be employed in reactive association with the emulsions, or in a processing bath prior to or during development of emulsion layers.
Description
United States Patent Baldassarri et al.
AZOTRIAZOLE AND AZOTETRAZOLE ANTIFOG, ANTISTAIN AND SELECTIVE DESENSITIZERS FOR SILVER HALIDE EMULSIONS Inventors: Agostino Baldassarri, Savona', Luigi Cellone, Albissola MarinaSavona, both of Italy Assignee: Minnesota Mining and Manufacturing Company, St. Paul, Minn.
Filed: Mar. 15, 1972 Appl. No: 235,011
Published under the Trial Voluntary Protest Program on January 28, 1975 as document no. B 235,011.
Foreign Application Priority Data Mar. 16, l97l ltaly 49093/71 US. Cl. 96/109; 96/665; 96/56 Int. Cl. G03C 11'34 Field of Search 96/109, 66.5, 66.4, 56;
Primary Examiner-Norman G. Torchin Assistant Examiner.lohr1 L. Goodrow Attorney, Agent, or Firm-Alexander, Sell, Steldt & DeLaHunt [57] ABSTRACT Azotriazoles and azotetrazoles are effective antifogging agents, antistain agents and selective desensitizers for silver halide photographic emulsions, Such agents may be employed in reactive association with the emulsions, or in a processing bath prior to or during development of emulsion layersv 12 Claims, No Drawings AZOTRIAZOLE AND AZOTETRAZOLE ANTIFOG, ANTISTAIN AND SELECTIVE DESENSITIZERS FOR SILVER HALIDE EMULSIONS The present invention relates to the use of azotriazoles and azotetrazoles as anti-fog, anti-stain and/or selective desensitizers for silver halides photographic emulsions.
Various compounds have long been employed to reduce fog and stain in silver halide emulsions. Certain of these compounds must be contacted with silver halide photographic emulsions in order to effectively inhibit fog; others are desirably employed in processing baths through which silver halide emulsions pass during or prior to development. Certain fog inhibiting compounds in addition tend to desensitize silver halide emulsions. Those desensitizers which desensitize silver halide only to radiation of certain wave lengths, for example, X-rays, are known as selective" desensitizers, and are particularly useful in silver halide radiographic emulsions.
Many of the compounds which can effectively inhibit fog are unfortunately incapable of similarly inhibiting stains (i.e., intense, localized fog centers). Further, certain fog-restraining compounds can be employed only in a silver halide photographic emulsion (US. Pat. No. 2,273,152), whereas other compounds can be employed only in photographic processing baths. Moreover, many fog inhibiting compounds do not function as selective desensitizers for silver halide emulsions. It would be highly desirable to provide a single class of compounds capable of restraining fog, restraining stains", and of selectively desensitizing silver halide emulsions.
It has now been found that azotriazole and azotetrazole compounds are capable of inhibiting fog when placed in contact with a silver halide emulsion (as by being placed in the emulsion, in a layer adjacent the emulsion, or by being placed in a processing bath which is employed prior to or during development of the emulsion). These compounds have also been found to inhibit stains in silver halide photographic emulsions, and, in larger quantities, to selectively desensitize silver halide emulsions.
Accordingly, in one embodiment the present invention relates to a silver halide photographic emulsion having contacted therewith at least a fog-inhibiting amount of an azotriazole or an azotetrazole. In another embodiment, the invention relates to a method for in hibiting fog in a silver halide photographic emulsion which comprises contacting the emulsion with an azotetrazole or an azotriazole. In yet another embodiment, the invention relates to an aqueous processing solution for silver halide photographic emulsions adapted for use prior to or during development and containing from about 3 to about 6 milligrams of an azotriazole or an azotetrazole per liter of solution.
The azotriazoles and azotetrazoles of the present invention preferably correspond to the formula 2 z' I c N N c N l N wherein Z and Z independently represent atoms forming heterocyclic nuclei of the triazole or tetrazole series. By azotriazole" and azotetrazole", reference is made to compounds which have respectively two triazole heterocyclic nuclei or two tetrazole heterocyclic nuclei, which nuclei are joined by an N=N linking group through carbon atoms thereof. These compounds may be variously substituted, and it has been found that azotriazoles and azotetrazoles as a class generally exhibit anti-fog, antistain and selective desensitization characteristics. In a preferred embodiment, sub stituents borne by the heterocyclic nuclei of the azotriazoles and azotetrazoles of the invention include hydrogen, alkyl (e.g., C,C alkyl), alkaline (e.g., C C and aryl (e.g., phenyl, naphthyl, including substituted aryl such as alkaryl having no more than 15 aliphatic carbon atoms, etc.). Accordingly, in a most preferred embodiment the azotriazoles and azotetrazoles of the present invention correspond to the formula wherein X is carbon or nitrogen, and each Y group independently represents a hydrogen atom, an alkyl group (e.g., C,C an alkaline group (e.g., C,C or an aryl group (e.g., phenyl, naphthyl, including substituted aryl such as alkaryl containing no more than 20 aliphatic carbon atoms), etc.
In comparison with known fog restrainers, the present invention permits a single class of fog restrainers to be used for many purposes. For example, the triazoles and tetrazoles of the invention are useful both in photographic silver halide emulsions, (e.g., mixed into the emulsion layer or employed in a layer adjacent the emulsion layer) and in photographic processing baths which, for example, are employed either prior to development (as a pre-bath), in the developing bath itself, etc. The azotriazole and azotetrazole compounds of the invention are particularly desirable because they are generally readily soluble in common photographic solvents such as water, alcohol, and aqueous alkaline solutions such as developer solutions. It will further be understood that it is most desirable to use highly soluble azotetrazoles or azotriazoles of the invention when they are to be employed in photographic processing baths, and to use the less soluble azotriazoles or azotetrazoles when they are to be used in an emulsion layer or in a layer adjacent an emulsion layer.
The invention may be more easily understood by reference to the following illustrative, non-limiting examples.
EXAMPLE 1 5,5'-azotetrazole-1,l 'pentahydrate disodium salt Na-N-CN=,N-CN-Na -5HO n l l 2 l N N N N N/ Analysis: Calculated Found EXAMPLE 2 5,5 'azotriazole hemihydrate NIT-C N N c ar i l l l l H N N N N H- H20 C 2 (prepared according to B. 26 2600 J. Thiele and K. Heidenrich) 8.4 g of 3-amino-l,2,4-triazole (0.] moles) were dissolved by boiling in l cc of H 0 containing 16 g (0.4 moles) of NaOH in a 300 cc flask equipped with mechanical stirrer and reflux apparatus. 5.4 g of KMnO in powder form were slowly added, with caution, to this solution. The excess oxidant was cautiously eliminated by addition of a few drops of ethanol. The mixture was filtered under vacuum and the yellow liquid obtained was acidified at C with glacial acetic acid. A very fine, pale-yellow powder was separated and collected by filtering and dried under vacuum. Yield: 2 g.
This compound can be usefully introduced into a photographic emulsion or photographic bath in aqueous solutions of sodium carbonate or NaOH.
- N N N A solution containing 9.8 g of amino-methyl-triazole (0.1 moles) prepared according to B. 26 2599, J. Thiele and K. Heidenreich), 16 g of NaOH (0.4 moles) and 100 cc of H 0, was brought to the boil in a 500 cc flask equipped with mechanical stirrer and reflux apparatus. Powdered KMnQ, was cautiously added in small amounts until the solution became permanently green (5.5 g of potassium permanganate). The excess oxidant was eliminated by addition of a few drops of ethanol. The separated brown manganese dioxide was filtered under vacuum. The cooled yellow solution was acidified (t 15C) with glacial acetic acid. A sulfur-yellow, very fine powder separated out and was filtered, dissolved in NHqOH, precipitated with CO and washed with H O. Yield: 2 g.
This compound can be usefully introduced into an emulsion or photographic bath in solutions of sodium carbonate or NaOH.
Analysis: Calculated Found N% 58.33 57.94 C% 37 .50 37.23 HFv 4.20 4. 3 1
EXAMPLE 4 l l '-diphenyl-5,5 'azotetrazole (prepared according to Journ. Prakt. 2, 134 282, R. Stolle).
20 g of l-phenyl-5-amino-tetrazole (prepared according to CA. 65 20137h, C.D. Bassinger and Takashi Enkoji) were dissolved in 500 cc of boiling water in a 2 liter flask equipped with a mechanical stirrer and reflux apparatus. Gaseous chlorine was passed through the boiling solution. After a few minutes an orange colored solid began to separate. After about 4 hours it was noticed that a further addition of chlorine did not cause separation of more solid. The solid was collected by hot filtration, washed with 500 cc of cold water and dried with air. Yield: 15 g. After crystallization of the product from 1500 cc of boiling glacial acetic acid, 12.5 g of felted orange needles, M.P. 227C. were obtained.
This compound can be usefully introduced into a photographic silver halide emulsion or into a photographic bath in ethanol of dimethylformamide solution.
(prepared according to J. Phys. Chem. 6], 265, M. M. Williams, W. S. McEvan and R. A. Henry).
20 g of lmethyl 5azotetrazole, prepared according to J.A.C.S. 76 923, R. A. Henry and W. G. Finnegan, were suspended in cc of water. 100 cc ofa 10% active chlorine sodium hypochlorite solution were added. The mixture was brought to the boil and maintained for minutes at this temperature. The resulting solution was allowed to cool in ice and was kept at 0C overnight. The yellowish solid which separated was filtered under vacuum, washed with water and dried under vacuum. Yield: 8 g. The product obtained was crystallized from 60 cc of boiling ethyl acetate. A yellow powder (6.2 g., MP. l-l22C) which according to the literature corresponds to a mixture of the cis" and trans forms, was obtained.
This compound can be usefully introduced into emulsions or photographic baths in ethanol solution.
10 g of 2-methyl-S-amino-tetrazole, suspended into 50 cc of H 0 were added to 50 cc of a 10% active chlo- 6 was washed with lOO cc of water and dried at 30C under vacuum. Yield: 5 g. M.P. 100C.
This compound can be usefully introduced into emulsions or photographic baths in ethanol solution.
Analysis: Calculated Found C% 38.99 38.49 H% 4.06 4.3! N% 56.85 56.25
EXAMPLE 8 2,2-diallyl-5 ,5 '-azotetrazole N--C N s l l CH =cH-cir -it n 3.13 g (0.025 moles) of 2-allyl-5-amino tetrazole dissolved in 50 cc of boiling water, were combined during a 10 minute period with stirring with 0.05 moles of sodium hypochlorite in a 8.5% active chlorine solution while keeping the mixture at boiling point. A crystalline rine sodium hypochlorite solution. An exothermic reyellow Solid .began immediaotely to separate The mixaction occurred and the mixture became orange in mm was rapldly cooled to 0 filters! under acuum color. The mixture was brought to the boil for 20 minwith 50 cc of cold water The residue was utes, and was then cooled in ice. After two hours the dried at Q c under l gof product were separated crystalline orange yenow solid (55 g.) was tamed, which were then dissolved in 45 cc of ethyl acefiltered off and crystallized from 45 cc of acetyl ace- The solvent Concentrated to 15 cc and tate 4 g of orange needles, MP. "0L1 were allowed to crystallize. 1.5 g of orange-yellow small neetained. dies, MP. 94-96C were obtained.
This compound can be usefully introduced into emul- Thls compound l be Introduced emul' sions or photographic baths in ethanol solution. 40 Slons or phowgraphlc baths m ethanol soluuon Analysis: Calculated Found Analysis: Calculated Found 5% 22.3% 23.3 c% 38.49 38.42 11% 4.06 4.21 N% 72.10 11.42 N% 56.89 56.28
EXAMPLE 7 EXAMPLE 9 1,1'-diallyl-5,5-azotetrazole For the compounds of example i to 8 and for the 5,5'-dichloro-2,2-azopyrine (compound C), suitable CH2 CH CH2 N a 5g solvents have been selected, and the solubility of these N L compounds at 20C in these solvents has been determined. The results are reported in the following table 1.
Table l N C--N -ca -CH -0H H Compound Solvent Solubility (weight N c Ethanol 0.0009 l Water l0 2 2% NaOH in water 10 3 2% NaOl-l in water 10 I 6.25 g of l-allyLS-amino-tetrazole (prepared accordg 3; ing to J.A.C.S. 76, 923, R. A. Henry and W. G. Finne- 6 Elha d 0.5 gan) were dissolved in 100 cc of water in a 500 cc flask 7 Ethanol equipped with a stirrer, reflux and dropping funnel. 8 While the solution was maintained at the boil, 0.1 moles of sodium hypochlonte (in a 8.5% active chlo- EXAMPLE 10 rine solution) were added over a period of 10 minutes with vigorous stirring. The mixture was allowed to cool slowly to room temperature, and was then filtered under vacuum. The orange solid which was obtained A high-sensitivity, physically seasoned, washed, and chemically sensitized silver bromo-iodide emulsion, containing 98.2 moles of bromide and 1.8 moles of iodide percent of halide, was divided in several portions to which were added respectively l'phenyl-S-mercaptotetrazole (labeled A), -methyl-benzotriazole (labeled B), and the compounds of Examples 1 to 8.
from a tungsten lamp, were developed at C in the respective developer portions for 3 minutes. 6 minutes and l2 minutes. The results of a densitometer reading of the developed samples are reported in table 3.
Each single portion was spread on a cellulose triace- 5 tate support and covered with a protective gelatin Table 3 Developer Relative Sensitivity Fog 3 min 6 min l2 min 3 min 6 min 12 min Control 100 95 90 0.21; 0.34 045 Control compound of Example N0. 2 00 73 73 0.17 0.l8 0.21
layer. Each of the resulting samples was exposed to EXAMPLE 12 light from a tungsten lamp and developed for 3 minutes E d h h at 20C in a developer of the following composition: Xample l 1 repeat? t at l samples of a seml-ammomacal, hlgh sensitlvity, silver 20 bromo-iodide emulsion, containing 98 mole bromide d2 ll'd'd 1 0D 't t Anhydrous sodium sun-e 50 8 an mo e 0 10 re were emp oye ensi ome ry re- Hydroquinone 9 g sults are reported In table 4.
Table 4 Developer Relative Sensitivity Fog 3 min 6 min 2 min 3 min 6 min l2 min Control 105 98 95 0.11; 025 036 Control compound of Example No. 2 68 76 75 0.13 0.l5 0.|8
Anhydrous sodium carbonate 50 8 Potassium bromide 3 g Water I0 1000 CC 3M Medical X-Ray Film, Type R, was exposed to gig gggg g $8 1; for the thus processed Samples blue light from a tungsten lamp and was divided into p two portions. One portion was developed for 30 min- Table 2 utes at 30C in the following developer. Compound uM/MA g Relative Sensitivity Fog Blank loo 028 Anhydrous sodium sulfite 2 g A l 100 (1-28 2-amino-5-N.N-etil-B-methan- A m 100 (1-28 sulfonamido-ethyl-toluene A 028 sulfonate 5.5 g A l0: l6 Dihydrate sodium metaborate g B 1 100 5 Sodium bromide 1.6 B loo Water to 1000 cc B 10 0.28 B 10 79 0.29 1 1.25 89 0.18 1 g i? 8-}; The remaining portion was identically developed in 2 -1 89 50 an identical developer which, however, additionally g g 5 2 3:2 contained 200 M per liter of the compound of Exam- 3 sI10- 85 0:18 P 2 3 1 75 0.17 The results of a densitometer readmg of the develw} '22 8f; oped samples are reported in table 5. 4 5.10 63 0.13 5 2.10- 75 0.20 55 Table 5 g f 32 8 if: Relative Sensitivity Fog 6 2J0 m0 (121 Control 0.23 0 10 34 0.15 532381; of 0 5.10 56 0.10 7 5.10 00 020 Example 2 0.03 a 10* 89 0.25
EXAMPLE ll EXAMPLE I4 65 Photographic material similar to that of Example 10 A quantity of the developer of Example 10 was divided into two portions. To one portion was added 50 42M of the compound of Example 2. Samples of the photographic material of Example [0, exposed to light was exposed to the light from a tungsten lamp and divided into three samples. One sample was developed in a developer of the following formula:
Metol 3 g Anhydrous sodium sulfite 50 g Hydroquinone 9 g Glutaraldehyde bisulfite 13 g Anhydrous sodium carbonate 50 g Potassium bromide 3 g Water to 1000 cc The second and third samples were identically developed, except that the developers for these samples contained respectively 50 pM per liter of the compouds of Examples 2 and 3.
Results of densitometer readings are reported in table 6.
Acetic acid to a pH 10.1
The second sample was identically developed except that the developer containing 200 p.M per liter of the compound of Example 2.
Results of -nsitometer readings are reported in table 7.
Table 7 Relative Sensitivity Fog Control 100 0.85 Control compound of Example No. 2 100 0.45
EXAMPLE 16 To samples of a medium sensitivity, physically seasoned, washed and chemically sensitized silver bromoiodide emulsion containing 97.5 moles of bromide and 2.5 mole of iodide, were added various amounts of compounds of the present invention, of red mercury iodide (a known selective desensitizer), and of l-phenyl-S-mercaptotetrazole (labeled A).
The resulting emulsions were then spread on cellulose triacetate supports, and samples of the corresponding materials were exposed to white light and to X-rays of various energy. The exposed samples were then developed for 3 minutes at 20C in the developer of Example 10.
Densitometry results are reported in table 8.
Table 8 Compound uM/MA g Relative Sensitivity Fog White R X light 67 K V 200 K V 100 100 100 0.27 l-lgl 0.5 71 100 90 0.25 Hgl 1.0 55 90 75 0.20 Hgl, 2.5 27 56 45 0.10 Hgl, 5.0 15 30 30 0.04 A 1.0 100 100 100 0.27 A 10.0 100 100 79 0.2, A 5.10 50 70 60 0.24 A 10 25 50 50 0.22 l 5.0 71 100 100 0.17 l 10 40 100 0.16 l 10 31 I00 83 0.08 l 5.10 5 50 38 0.04 2 5.10 50 89 89 0.10 2 10 25 70 70 0.08 2 2.5.10" 5 50 40 0.04 3 10 71 105 0.06 3 10 45 100 7] 0.06 3 2.5.10 10 71 50 0.04 6 10 63 100 0.08 6 10 31 89 89 0.04 7 10 50 100 89 0.08 7 10 31 E9 89 0.04 8 2 5.10 25 63 25 0.13
EXAMPLE 17 A cellulose triacetate support was thinly coated with gelatin containing powdered iron. Three samples of the resulting material, drawn at random, were each divided into four parts. On the first part a high sensitivity, silver bromo-iodide containing 98 moles of bromide and 2 mole of iodide were coated. On the other three parts of each sample, the same emulsion to which had been added respectively the compounds of Examples 1 and 2 and the 1-phenyl-S-mercapto-tetrazole (labeled A) were coated. On each element thus obtained a protective gelatin layer was coated. The resulting elements were kept 10 minutes in a cold state and were then developed 10 minutes at 20C in the developer of Example 10. The white and black points on each of the resulting elements were counted.
The results are given in table 9.
Table 9 No. of No. of No. of Compound pM/MAg Points Points Points Sample 1 Sample 2 Sample 3 150 103 89 1 102 91 Ex 1 1.5 15 17 7 Ex. 05 20 30 l 5 EXAMPLE 18 Phenidone 0.3 g Anhydrous sodium sulfite 50.0 g Hydroquinone 9.0 g
-continued Glutaraldehyde bisulfite 13.0 g Anhydrous sodium carbonate 50.0 g Potassium bromide 3.0 g Water to 1000 cc According to the time and temperature indicated in table below.
The developed material was fixed in a bath of the following composition: 10
Anhydrous sodium sulfite 50.0 g Pentahydrate sodium thiosulfate 400.0 g Glutaraldehyde bisulfite l3.0 g Water to 1000 cc and washed for a total processing time of 90 seconds. Densitometer readings are reported in table 10.
Table 10 Compound uM/MAg Developing Developing Relative Fog bath temp- Time Sensiti erature vity Control C 23 sec. 100 0.26 Ex. 2 6.25.10 35C 23 sec. 89 0.l4 Control 318C 23 sec. H2 038 Ex. 2 6.25.10" 318C 23 sec. 93 026 Control 406C 23 sec. ll2 0.56 Ex. 2 625.10" 406C 23 sec. 102 0.38
The silver halide photographic emulsions of the pres- 30 ent 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 pyrolidone, partially hy- 3 drolyzed polyvinyl acetate, polyethylacrylate, polymethylmethacrylate, polyamides, etc. The emulsions of the invention may be chemically sensitized with naturally active gelatin, by addition of chemical sensitizers such as thiourea, allylthiourea, thiocyanates, thiosulfates, etc. Sensitization may be effected by the addition of noble metals, such as gold salts. Spectral sensitizers may be employed in emulsions of the invention, such as cyanine and merocyanine dyes. Moreover, the emulsions of the invention may include such additives as color couplers, filtering dyes, surfactants, hardeners, stabilizers, additional fog-restrainers, plasticizers, oxidizing agents, developing accelerators, etc. To form a photographic element, the emulsions of the invention may be coated upon any convenient support such as polyester, cellulose acetate, and the like.
The azotriazoles and azotetrazoles of the invention may be conveniently introduced in the form of solutions into emulsions during preparation thereof. Although it is generally preferred to incorporate the azotriazole and azotetrazole 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 in contact therewith. As antifog and antistain agents, the azotriazoles and azotetrazoles of the invention are preferably used in amounts ranging from about 0.03 mg. to
12 about 0.2 mg. per kilogram of emulsion, and as selective desensitizers these compounds are preferably used in amounts ranging from 3 to mg. per kilogram of emulsion.
The processing baths of the present invention, as noted previously, may be photographic pre-baths, such as those known to the art to be useful prior to treatment of a photographic emulsion with a developing solution. Predevelopment baths usually (but not necessarily) are acidic and may contain hardeners such as aldehydes and the like. The azotriazole and azotetrazole 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, metol-hydroquinone, phenidone, hydroquinonephenidone, and various p-phenylene diamine materials,
the latter being useful in color development processes. The processing baths of the invention (pre baths and developer baths) preferably employ from 3 to about 60 milligrams of azotriazole or azotetrazole compound per liter of solution.
What we claim is:
1. A silver halide photographic emulsion having contacted therewith at least a fog-inhibiting amount of an azotriazole or an azotetrazole.
2. The emulsion of claim 1 wherein said anti-fogging agent is a 5,5'-azotetrazole-l,l '-disodium salt.
3. The emulsion of claim 1 wherein said anti-fogging agent is a 5,5'-azotriazole.
4. The emulsion of claim 1 wherein said anti-fogging agent is a 3,3'-dimethyl-5,5'-azotriazole.
5. The emulsion of claim 1 wherein said anti-fogging agent is a 1,1'-diphenyl5,5'-azotetrazole.
6. The emulsion of claim 1 wherein said anti-fogging agent is a 1,1 '-dimethyl-5,5-azotetrazole.
7. The emulsion of claim 1 wherein said anti-fogging agent is a 2,2'-dimethyl-5,S-azotetrazole.
8. The emulsion of claim 1 wherein said anti-fogging agent is a 1,1'-diallyl-5,5'-azotetrazole.
9. The emulsion of claim 1 wherein said anti-fogging agent is a 2,2'-diallyl-5,5'-azotetrazole.
10. A method for inhibiting fog in a silver halide photographic emulsion which comprises contacting said emulsion with an azotetrazole or an azotriazole.
11. A method for inhibiting fog and stain in a silver halide emulsion which comprises contacting said emulsion with an azotriazole or an azotetrazole.
12. The emulsion of claim 1 wherein there is a fog inhibiting amount of azotriazole contacted therewith.
Claims (12)
1. A SILVER HALIDE PHOTOGRAPHIC EMULSION HAVING CONTACTED THEREWTIH AT LEAST A FOG-INHIBITING AMOUNT OF AN AZOTRIAZOLE OR AN AZOTETRAZOLE.
2. The emulsion of claim 1 wherein said anti-fogging agent is a 5,5''-azotetrazole-1,1''-disodium salt.
3. The emulsion of claim 1 wherein said anti-fogging agent is a 5,5''-azotriazole.
4. The emulsion of claim 1 wherein said anti-fogging agent is a 3,3''-dimethyl-5,5''-azotriazole.
5. The emulsion of claim 1 wherein said anti-fogging agent is a 1,1''-diphenyl-5,5''-azotetrazole.
6. The emulsion of claim 1 wherein said anti-fogging agent is a 1,1''-dimethyl-5,5''-azotetrazole.
7. The emulsion of claim 1 wherein said anti-fogging agent is a 2,2''-dimethyl-5,5''-azotetrazole.
8. The emulsion of claim 1 wherein said anti-fogging agent is a 1,1''-diallyl-5,5''-azotetrazole.
9. The emulsion of claim 1 wherein said anti-fogging agent is a 2,2''-diallyl-5,5''-azotetrazole.
10. A method for inhibiting fog in a silver halide photographic emulsion which comprises contacting said emulsion with an azotetrazole or an azotriazole.
11. A method for inhibiting fog and stain in a silver halide emulsion which comprises contacting said emulsion with an azotriazole or an azotetrazole.
12. The emulsion of claim 1 wherein there is a fog-inhibiting amount of azotriazole contacted therewith.
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US235011A Expired - Lifetime US3925086A (en) | 1971-03-16 | 1972-03-15 | Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions |
Country Status (9)
Country | Link |
---|---|
US (1) | US3925086A (en) |
JP (1) | JPS5547374B1 (en) |
AR (1) | AR204386A1 (en) |
BE (1) | BE780718A (en) |
CA (1) | CA1007092A (en) |
CH (1) | CH588092A5 (en) |
DE (1) | DE2212550A1 (en) |
FR (1) | FR2130240B1 (en) |
GB (1) | GB1383211A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4046571A (en) * | 1975-06-27 | 1977-09-06 | Gaf Corporation | Processing solution for use as photographic developer bath and replenisher therefor |
WO2014127297A1 (en) | 2013-02-15 | 2014-08-21 | Cambrios Technologies Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
US10720257B2 (en) | 2013-02-15 | 2020-07-21 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
US10971277B2 (en) | 2013-02-15 | 2021-04-06 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5753327A (en) * | 1980-09-17 | 1982-03-30 | Ekuseru Kk | Preparing device of hollow molded object having bent part |
JPS5770622A (en) * | 1980-10-22 | 1982-05-01 | Ekuseru Kk | Manufacture of foamed synthetic resin hollow molded article |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2453087A (en) * | 1946-11-07 | 1948-11-02 | Gen Aniline & Film Corp | Photographic developers containing tetrazolyl disulfides as antifogging agents |
US2588538A (en) * | 1948-08-06 | 1952-03-11 | Ilford Ltd | Stabilizers in photographic emulsions and developers |
US3563747A (en) * | 1966-11-04 | 1971-02-16 | Agfa Gevaert Nv | Photographic developing combinations |
US3615616A (en) * | 1967-10-09 | 1971-10-26 | Agfa Gevaert Nv | Photographic light-sensitive silver halide material |
US3719604A (en) * | 1970-02-03 | 1973-03-06 | Dynamit Nobel Ag | Pressurizing-gas-producing charges containing an aminoguanidine tetrazole and an oxygen-liberating or gas-evolving additive |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR810104A (en) * | 1935-08-16 | 1937-03-15 | Ilford Ltd | Improvements to dyeing materials |
-
1972
- 1972-01-01 AR AR240968A patent/AR204386A1/en active
- 1972-03-07 CH CH333972A patent/CH588092A5/xx not_active IP Right Cessation
- 1972-03-14 GB GB1190172A patent/GB1383211A/en not_active Expired
- 1972-03-15 US US235011A patent/US3925086A/en not_active Expired - Lifetime
- 1972-03-15 FR FR7208936A patent/FR2130240B1/fr not_active Expired
- 1972-03-15 DE DE19722212550 patent/DE2212550A1/en active Granted
- 1972-03-15 BE BE780718A patent/BE780718A/en not_active IP Right Cessation
- 1972-03-15 JP JP2650572A patent/JPS5547374B1/ja active Pending
- 1972-03-15 CA CA137,175A patent/CA1007092A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2453087A (en) * | 1946-11-07 | 1948-11-02 | Gen Aniline & Film Corp | Photographic developers containing tetrazolyl disulfides as antifogging agents |
US2588538A (en) * | 1948-08-06 | 1952-03-11 | Ilford Ltd | Stabilizers in photographic emulsions and developers |
US3563747A (en) * | 1966-11-04 | 1971-02-16 | Agfa Gevaert Nv | Photographic developing combinations |
US3615616A (en) * | 1967-10-09 | 1971-10-26 | Agfa Gevaert Nv | Photographic light-sensitive silver halide material |
US3719604A (en) * | 1970-02-03 | 1973-03-06 | Dynamit Nobel Ag | Pressurizing-gas-producing charges containing an aminoguanidine tetrazole and an oxygen-liberating or gas-evolving additive |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4046571A (en) * | 1975-06-27 | 1977-09-06 | Gaf Corporation | Processing solution for use as photographic developer bath and replenisher therefor |
WO2014127297A1 (en) | 2013-02-15 | 2014-08-21 | Cambrios Technologies Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
EP3598185A2 (en) | 2013-02-15 | 2020-01-22 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
US10720257B2 (en) | 2013-02-15 | 2020-07-21 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
US10971277B2 (en) | 2013-02-15 | 2021-04-06 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
Also Published As
Publication number | Publication date |
---|---|
CH588092A5 (en) | 1977-05-31 |
AR204386A1 (en) | 1976-02-06 |
DE2212550A1 (en) | 1972-11-02 |
JPS5547374B1 (en) | 1980-11-29 |
DE2212550C2 (en) | 1987-02-12 |
CA1007092A (en) | 1977-03-22 |
GB1383211A (en) | 1975-02-05 |
FR2130240A1 (en) | 1972-11-03 |
BE780718A (en) | 1972-09-15 |
USB235011I5 (en) | 1975-01-28 |
FR2130240B1 (en) | 1975-10-24 |
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