US2819965A - Carboxymethylmercapto compounds as stabilizers for photographic emulsions - Google Patents
Carboxymethylmercapto compounds as stabilizers for photographic emulsions Download PDFInfo
- Publication number
- US2819965A US2819965A US567418A US56741856A US2819965A US 2819965 A US2819965 A US 2819965A US 567418 A US567418 A US 567418A US 56741856 A US56741856 A US 56741856A US 2819965 A US2819965 A US 2819965A
- Authority
- US
- United States
- Prior art keywords
- emulsions
- carboxymethylmercapto
- compounds
- photographic
- grams
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title claims description 64
- -1 Carboxymethylmercapto compounds Chemical class 0.000 title claims description 46
- 239000003381 stabilizer Substances 0.000 title description 4
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 11
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 24
- 239000000243 solution Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 230000000087 stabilizing effect Effects 0.000 description 8
- 150000001340 alkali metals Chemical group 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 241000282320 Panthera leo Species 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- QCAWOHUJKPKOMD-UHFFFAOYSA-N 4,6-diamino-1h-pyrimidine-2-thione Chemical compound NC1=CC(N)=NC(S)=N1 QCAWOHUJKPKOMD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229940089960 chloroacetate Drugs 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000000586 desensitisation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- MPNBXFXEMHPGTK-UHFFFAOYSA-N pyrimidine-4,5,6-triamine Chemical compound NC1=NC=NC(N)=C1N MPNBXFXEMHPGTK-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- 150000003920 1,2,4-triazines Chemical class 0.000 description 1
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- VTSWSQGDJQFXHB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylpyrimidine Chemical compound CC1=C(Cl)N=C(Cl)N=C1Cl VTSWSQGDJQFXHB-UHFFFAOYSA-N 0.000 description 1
- ZZUQWNYNSKJLPI-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-ylsulfanyl)acetic acid Chemical compound C1=CC=C2SC(SCC(=O)O)=NC2=C1 ZZUQWNYNSKJLPI-UHFFFAOYSA-N 0.000 description 1
- MZIJIHZQKNAQBF-UHFFFAOYSA-N 2-(1,3-benzoxazol-2-ylsulfanyl)acetic acid Chemical compound C1=CC=C2OC(SCC(=O)O)=NC2=C1 MZIJIHZQKNAQBF-UHFFFAOYSA-N 0.000 description 1
- UYNVBLJQBCTRKV-UHFFFAOYSA-N 2-(1h-benzimidazol-1-ium-2-ylsulfanyl)acetate Chemical compound C1=CC=C2NC(SCC(=O)O)=NC2=C1 UYNVBLJQBCTRKV-UHFFFAOYSA-N 0.000 description 1
- JKAISOKGXPAILZ-UHFFFAOYSA-N 2-(4,6-diaminopyrimidin-2-yl)sulfanylacetic acid Chemical compound NC1=CC(N)=NC(SCC(O)=O)=N1 JKAISOKGXPAILZ-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
- NIEOYUNNKKAQKI-UHFFFAOYSA-N 2-pyrimidin-2-ylsulfanylacetic acid Chemical compound OC(=O)CSC1=NC=CC=N1 NIEOYUNNKKAQKI-UHFFFAOYSA-N 0.000 description 1
- VXEUGLRMYAXWKM-UHFFFAOYSA-N 3-phenyl-1h-imidazole-2-thione Chemical compound S=C1NC=CN1C1=CC=CC=C1 VXEUGLRMYAXWKM-UHFFFAOYSA-N 0.000 description 1
- OKNHZPGPLNUEPC-UHFFFAOYSA-N 4-amino-3-phenyl-1h-1,2,4-triazole-5-thione Chemical compound NN1C(S)=NN=C1C1=CC=CC=C1 OKNHZPGPLNUEPC-UHFFFAOYSA-N 0.000 description 1
- YFYYRKDBDBILSD-UHFFFAOYSA-N 6-amino-2-sulfanylidene-1h-pyrimidin-4-one Chemical compound NC1=CC(=O)NC(=S)N1 YFYYRKDBDBILSD-UHFFFAOYSA-N 0.000 description 1
- NKOPQOSBROLOFP-UHFFFAOYSA-N 6-methyl-3-sulfanylidene-2h-1,2,4-triazin-5-one Chemical compound CC1=NNC(=S)NC1=O NKOPQOSBROLOFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101100165177 Caenorhabditis elegans bath-15 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FZQDYEPVHITTBB-UHFFFAOYSA-N Cl[Br][I][Ag] Chemical compound Cl[Br][I][Ag] FZQDYEPVHITTBB-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002731 mercury compounds Chemical class 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- MISVBCMQSJUHMH-UHFFFAOYSA-N pyrimidine-4,6-diamine Chemical compound NC1=CC(N)=NC=N1 MISVBCMQSJUHMH-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940063675 spermine Drugs 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/48—Two nitrogen atoms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J3/00—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
- A61J3/07—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D233/30—Oxygen or sulfur atoms
- C07D233/42—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members 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
- C07D233/84—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/38—One sulfur atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/50—Three nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/56—One oxygen atom and one sulfur atom
-
- 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
- C07D249/12—Oxygen or sulfur atoms
-
- 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
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members 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
- C07D253/075—Two hetero atoms, in positions 3 and 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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
- 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
- C07D277/70—Sulfur atoms
- C07D277/74—Sulfur atoms substituted by carbon 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
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
- G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
Definitions
- Fog depends both on the emulsion and the conditions of development; for a given emulsion it increases with the degree of development. With constant development conditions, it tends to increase with time, temperature and relative humidity of storage conditions; it is common practice to make accelerated tests of the stability of photographic emulsions by storage at increased temperature or humidity, or both. It 1s, of course, desirable to have emulsions as stable as possible under the conditions of high temperature and humidity which may occur in tropical climates, for example. Fog usually appears over the whole area of the sensitive coating, but when severe, it frequently is non-uniform. Fog may also be caused by exposure to chemicals, for example, hydrogen sulfide and other reactive sulfur compounds, hydrogen peroxide vapor, and strongly reducing materials.
- antifoggants and stabilizers may protect, to some extent, against such efiects, it is normally understood that an antifoggant protects against spontaneous growth of fog during prolonged storage or storage at high temperatures and humidities, or during development to maximum contrast and speed, or both.
- an object of the present invention to provide a method for stabilizing photographic emulsions.
- a further object is to provide a means for reducing the fog produced upon keeping of such emulsions which have been sensitized, especially emulsions stored under tropical or other adverse conditions.
- a still further object is to provide a means for stabilizing the speed and contrast of sensitized photographic emulsions.
- heterocyclic nitrogen compounds containing a carboxymethylmercapto substituent have strong antifoggant and stabilizing effects when incorporated in photographic silver halide emulsions.
- the optimum concentrations are generally higher than those of the corresponding mercaptans and are less critical with respect to desensitization.
- Many of our antifoggant and stabilizing compounds have a sulfur or oxygen atom in the heterocyclic ring, in addition to the nitrogen atom.
- simple heterocyclic compound we mean a compound wherein the heterocyclic atoms (i. e. atoms other than carbon) are members of a single heterocyclic ring, as contrasted with compounds containing fused or condensed heterocyclic rings in which the heterocyclic atoms are members of more than one heterocyclic ring.
- Such simple heterocyclic nitrogen compounds include triazoles (e. g. 1,2,4-triazoles, especially those containing an amino substituent in addition to the carboxymethylmercapto substituent), diazoles (e.
- R 1 N C-S- H-COOM wherein R represents a hydrogen atom or an alkyl group (e. g., methyl, ethyl, butyl, heptyl, etc.), M represents a hydrogen atom or an alkali metal atom (e. g., sodium, potassium, etc.), and Z represents the non-metallic atoms necessary to complete a simple heterocyclic ring as defined above.
- R represents a hydrogen atom or an alkyl group (e. g., methyl, ethyl, butyl, heptyl, etc.)
- M represents a hydrogen atom or an alkali metal atom (e. g., sodium, potassium, etc.)
- Z represents the non-metallic atoms necessary to complete a simple heterocyclic ring as defined above.
- alkyl e. g., methyl, ethyl, butyl, heptyl, etc.
- the principal purpose of our invention is to provide a means for maintaining the sensitivity and fog of silver halide emulsions at or close to initial optimum values under conditions of high temperature or high humidity, or both.
- the antifoggants of our invention are added to the emulsion at any stage during the process of manufacture prior to coating the emulsion.
- the antifoggants can be added to the emulsion in solution in water or any convenient solvent not injurious to the emulsion, such as lower aliphatic alcohols, acetone, etc.
- solutions of antifoggants which we employ when added in suitable concentration before coating to unsensitized or optically sensitized silver halide emulsions usually do not appreciably afiect the sensitivity and fog when measurements are made soon after coating. However, when sensitometric measurements are made after appreciable intervals of time under tropical or dry conditions of storage at elevated temperatures, the antifoggants do stabilize speed and maintain fog at a low level.
- the preparation of silver halide emulsions involves three separate operations: (1) the emulsification and digestion or ripening of the silver halide, (2) the freeing of the emulsion from aqueous soluble salts usually by washing, (3) the second digestion or after-ripening to obtain increased sensitivity (Mees, The Theory of the Photographic Process, 1942, page 3).
- the fog inhibiting agents can be added at any stage, preferably after the final digestion.
- the photographic emulsions which we use are of the developing-out type and best results have been obtained with gelatino-silver bromoiodide emulsions. sions of varying halide composition can be used.
- the emulsions can be chemically sensitized by any of the accepted procedures.
- the emulsions can be digested With naturally active gelatin, or sulfur compounds may be added such as those described in Sheppard U. S. Patent 1,574,944 and U. S. 1,623,499, and Sheppard and Brigham U. S. Patent 2,410,689.
- the emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum, all of which belong to group VIH of the. periodic table of elements and have an atomic weight greater than 100.
- Representative compounds are. ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for sensitizing in amounts below that which produces anysubstantial fog inhibition, as described in Smith and Trivelli U. S. Patent 2,448,060, and as anti-foggants in higher amounts, as described in Trivelli and Smith U. S. Patents 2,556,245 and 2,566,263.
- the emulsions can also be chemically sensitized with gold salts as described in Waller and Dodd U. S. Patent 2,399,083, or stabilized with gold salts as described in Damschroder U. S. Patent 2,597,856 and Yutzy and Leermakers U. S. Patent 2,597,915.
- Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and Z-aurosulfobenzothiazole methochloride.
- the emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U. S. application Serial No. 319,611 (nowU. S. Patent 2,728,663, issued December 27, 1955); Carroll and Murray U. S. application Serial No. 319,612 (now U. S. Patent 2,728,664, issued December 27, 1955); and Leubner and Murray U. S. application SerialNo. 319,613 (now U. S. Patent 2,728,665, issued December 27, 1955), all filed November 8, 1952.
- the antifoggants of our invention are effective in the presence or absence of optical sensitizing dyes. Since optical sensitizing can atfect stability of emulsions with respect to sensitivity, fog and latent image changes, the action of the antifoggants is not completely independent of optical sensitizing or other emulsion variables. We have found, however, that both unsensitized emulsions and emulsions sensitized with cyanine or merocyanine dyes, or both, can be treated with the antifoggant comspeed,,gamma and fog, before and after incubation of each of the samples, are given in the following table. Kodak Developer D-19 has the following composition:
- Kodak Developer SD-28 has the following composition:
- the quanuty of antifoggant compound employed can N- nethyl-p-ammophenol sulfate 1.5 be vaned, dependmg upon the particular silver hahde Hydroqumone 1.3 employed, degree of ripening, presence or absence of Sodium sulfite (des1ccated) 75 other emulsion addenda, etc.
- the quanuty of Borax 4.5 anhfoggant can vary from about 0.01 to 3.0 grams per Potassmm brom1de 0.4 gram mole of s1lver halide 1n the emulsion.
- the stabilizing action afiorded by the antifoggants of our invention was determined by incubation of the emulsions for a period of 1 to 2 weeks at 120 F. (as indicated below) and at constant humidity. The speeds were measured in terms of 30/E Where E is the exposure in meter candle seconds required to produce a density of 0.2 above fog.
- the antifoggants were added to a panchromatically-sensitized, high speed silver bromiodide emulsion which had been chemically sensitized with a sulfur compound, such as described in Sheppard U. S. Patent 1,574,944 and potassium chloroaurate.
- the emulsions were then coated on a cellulose acetate support and the coatings exposed on an Eastman lb Sensitometer and processed for the time indicated below in a developer of the type indicated below. The results of these tests for to stabilize photographic silver halide emulsions, either in the presence or absence of chemical sensitizers.
- these antifoggants can be incorporated in a colloid layer, such as a gelatin overcoating layer or interlayer, in contact with the emulsion.
- the fog-inhibiting agents which we have described can be used in various kinds of photographic emulsions. In addition to being useful in non-sensitized emulsions, they can also be used in orthochromatic, panchromatic, and X-ray emulsions. if used with sensitizing dyes they can be added to the emulsion before or after the dyes are added.
- Various silver halides can be used as the lightsensitive material, including silver bromide, silver iodide, silver chloride, silver bromiodide, silver chlorobromide, silver chlorobromiodide, etc.
- the antifoggants of our .7 invention cantbe used in emulsions intended for color photography, for example, emulsions containing colorforming couplers, or emulsions to be developed by solutions containing couplers.
- the dispersing agents can be gelatin, or other colloids, such as collodion, albumen, cellulose derivatives, synthetic resins, etc.
- carboxymethylrnercapto compounds can, as mentioned above, be obtained from the corresponding mercapto compounds by condensing an alkali metal salt of the mercapto compound with an alkaline solution containing an alkali metal chloroacetate.
- This method of making the carboxymethylmereapto compounds of our invention is illustrated in U. S. Patent 2,527,265, issued October 24, 1950. Other examples follow.
- Example A -2 carboxymethylmercapto-I -phenylz'midazole KIJaHs HC-N
- a mixture of 3.5 grams of 1-phenyl-2(3H)-imidazolethione, 3.0 grams of sodium chloroacetate and 15 ml. of water was heated on the water bath for 15 minutes, then 2.0 grams of sodium carbonate was added, and the mixture refluxed 0.5 hour. The clear solution was filtered, and acetic acid was added. The product separated as a white precipitate which was filtered, washed and dried. Yield, 3.5 grams, M. P. l48-50 C.
- Z-carboxymethylmercapto 4,5,6 triaminopyrimidine (compound 8) was prepared by replacing the pyrimidine compound used in Example B by a molecularly equivalent amount of 2-mercapto-4,S,6-triaminopyrimidine.
- Example C.2-carboxymethylmercapro 4 amino-fi-hydroxypyrimidine N ?NH: HOOGCHzS-(J CH N-c-OH
- Example D.2-carboxymethylmercaptopyrimidine li H A mixture of 4.0 grams of Z-mercaptopyrimidine and 4.5 grams of sodiumchloroacetate in 50 ml. of water was heated on the steam bath 15 minutes, 3.5 grams of sodium bicarbonate added, and the heating continued one hour. After cooling, the solution was acidified with hydrochloric acid, and the solid collected and recrystallized from water to give 1.5 grams of the product, M. P. 198-200 C.
- Hi l -SCH2CO0H H0C N
- Example F --2-carboxymethylmercaptobenzoxazale C-SCHgCO OH
- a mixture of 15.1 grams of Z-mercaptobenzoxazole and 13.0 grams of sodium chloroacetate in ml. of water was heated to reflux, and dilute sodium bicarbonate was slowly added until solution was complete, then refluxed for 10 minutes. The clear, yellow solution was filtered hot, and the filtrate was acidified with acetic acid. A nicely crystalline, yellow precipitate slowly separated from the aqueous phase. After standing overnight, the precipitate was collected by filtration and dried to give 12 grams of product, M. P. 1645 C.
- 2-carboxymethylmercaptobenzothiazole (compound 16) was prepared by replacing the Z-mercaptobenzoxazole employed in Example F by a molecularly equivalent amount of 2-mercaptobenzothiazole.
- the desired product was obtained as crystals melting at 162-3 C.
- Example H -carboxymethylmercapto-3,4-diamin0-1,2, 4-triaz0le l o-somooon
- Example ]-2-carboxymezhylmercapt0-4,6-diaminas-triazine acetic acid were then added to the colorless solution with stirring until solution was obtained. The clear solution was then stirred for an additional 21 hours, no change in appearance taking place during this time. A small amount of activated carbon and a filtering agent were added to the clear solution, which was then filtered. The clear filtrate was acidified with dilute acetic acid to give a white precipitate. This precipitate was collected on a filter and dried. Yield, 5.7 g. (94.5%). A small amount of the solid was recrystallized in sodium hydroxide solution, filtered, and reprecipitated in acetic acid. The dried product had a decomposition point of about 250 C.
- compound 4 was obtained by heating together 102 g. of Z-mercaptoimidazoline and g. of sodium chloroacetate in 200 cc. of water. 102 g. of the desired product were obtained. In like manner, compound 3 was obtained from the corresponding mercapto compound. See Johnson and Edens-JACS, vol. 64 (1942), page 2708).
- carboxymethylmercapto compounds of our invention can also be employed to advantage as stabilizers in photographic silver halide emulsions.
- compounds containing a carbalkoxylmethylmercapto group or a carbamylmethylmercapto group can sometimes be employed to advantage in photographic emulsions.
- the following two examples will describe the preparation of two compounds of these types which can be employed to advantage in photographic emulsions.
- Example N.2-carbethoxymethylmercaptoimidazolium hydrochloride 2O C-SOHiCOOCzHr A mixture of 10.2 g. of ethylenethiourea and 13.0 g. (11.3 ml.) of ethyl chloroacetate in 30 ml. of absolute alcohol was refluxed for 3 hours after which 60 ml. of acetone was added to the reaction mixture. The product which had separated was filtered off and recrystallized from isopropanol to give 21 g. of Z-carbethoxymethylmercaptoimidazolium hydrochloride, M. P. 1423 C.
- antifoggant and stabilizing compounds of our invention which contain a benzene ring can have substituents on the benzene ring, such as chlorine, bromine, methyl, ethyl, phenyl, etc. These compounds can be prepared in exactly the manner shown in the above examples.
- a photographic silver halide emulsion containing a monoheterocyclic nitrogen compound selected from those represented by the following general formula:
- R represents a member selected from the group consisting of a hydrogen atom and an alkyl group
- M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom
- Z represents the non-metallic atoms necessary to complete a heterocyclic ring.
- V N o-s-omooon wherein M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete an imidazoline heterocyclic ring.
- M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a pyrimidine heterocyclic ring.
- M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a 1,2,4-triazine heterocyclic ring.
- M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a benzoxazole heterocyclic ring.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Public Health (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Plural Heterocyclic Compounds (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE555210D BE555210A (US07166745-20070123-C00016.png) | 1956-02-23 | ||
US567418A US2819965A (en) | 1956-02-23 | 1956-02-23 | Carboxymethylmercapto compounds as stabilizers for photographic emulsions |
FR1173222D FR1173222A (fr) | 1956-02-23 | 1957-02-20 | Nouveau produit photosensible |
GB6176/57A GB859143A (en) | 1956-02-23 | 1957-02-25 | Photographic silver halide emulsions containing fog inhibiting or stabilizing agents |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US567418A US2819965A (en) | 1956-02-23 | 1956-02-23 | Carboxymethylmercapto compounds as stabilizers for photographic emulsions |
Publications (1)
Publication Number | Publication Date |
---|---|
US2819965A true US2819965A (en) | 1958-01-14 |
Family
ID=24267063
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US567418A Expired - Lifetime US2819965A (en) | 1956-02-23 | 1956-02-23 | Carboxymethylmercapto compounds as stabilizers for photographic emulsions |
Country Status (4)
Country | Link |
---|---|
US (1) | US2819965A (US07166745-20070123-C00016.png) |
BE (1) | BE555210A (US07166745-20070123-C00016.png) |
FR (1) | FR1173222A (US07166745-20070123-C00016.png) |
GB (1) | GB859143A (US07166745-20070123-C00016.png) |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2919985A (en) * | 1958-08-15 | 1960-01-05 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsions |
US2939789A (en) * | 1958-06-06 | 1960-06-07 | Gen Aniline & Film Corp | Fog reduction in photographic silver halide emulsions |
US2948615A (en) * | 1958-03-13 | 1960-08-09 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsions |
US2952539A (en) * | 1958-10-23 | 1960-09-13 | Gen Aniline & Film Corp | Photographic emulsions and developers stabilized with purine compounds |
US2976152A (en) * | 1958-12-19 | 1961-03-21 | Gen Aniline & Film Corp | Photographic gelatin layers containing triazine hardeners |
US2981624A (en) * | 1957-06-05 | 1961-04-25 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsion |
US3042521A (en) * | 1957-12-26 | 1962-07-03 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsion |
US3051570A (en) * | 1958-10-01 | 1962-08-28 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsions |
US3068239A (en) * | 1959-12-28 | 1962-12-11 | Monsanto Chemicals | Benzothiazole-, benzoxazole- and benzimidazole-2-thioacrylates and process |
US3081170A (en) * | 1958-10-06 | 1963-03-12 | Gen Aniline & Film Corp | Fog reduction in photographic silver halide emulsions |
US3084044A (en) * | 1960-12-09 | 1963-04-02 | Gen Aniline & Film Corp | Nitrogenous heterocyclic carboxyal-kylmercapto polyoxyalkylene ester photographic sensitizer |
US3136689A (en) * | 1959-12-28 | 1964-06-09 | Monsanto Co | Heterocyclic esters effective against micro-organisms |
US3220839A (en) * | 1961-08-25 | 1965-11-30 | Eastman Kodak Co | Photographic emulsions containing isothiourea derivatives |
US3252799A (en) * | 1962-06-09 | 1966-05-24 | Agfa Ag | Stabilized silver halide emulsions |
US3325287A (en) * | 1963-11-26 | 1967-06-13 | Fuji Photo Film Co Ltd | Photographic gelatin hardening composition |
US3365294A (en) * | 1963-04-27 | 1968-01-23 | Agfa Ag | Photographic material containing yellow fog-preventing agents |
DE2222297A1 (de) * | 1971-05-11 | 1972-11-23 | Agfa Gevaert Ag | Photographisches Silberhalogenidmaterial |
JPS4972735U (US07166745-20070123-C00016.png) * | 1972-10-14 | 1974-06-24 | ||
US3896129A (en) * | 1972-03-31 | 1975-07-22 | American Home Prod | (2-pyrimidinylthio) alkanoic acids, esters, amides and hydrazides |
US3901887A (en) * | 1972-03-31 | 1975-08-26 | American Home Prod | (2-pyrimidinylthio) alkanoic acids, esters, amides and hydrazides |
US3940394A (en) * | 1972-03-31 | 1976-02-24 | Santilli Arthur A | 2-pyrimidinylthio)alkanoic acids, esters, amides and hydrazides |
US4009029A (en) * | 1973-06-05 | 1977-02-22 | Eastman Kodak Company | Cyanoethyl-containing blocked development restrainers |
US4111697A (en) * | 1976-03-29 | 1978-09-05 | Agfa-Gevaert, N. V. | Novel antifogging and/or stabilizing compounds for silver halide photography |
US4116697A (en) * | 1976-12-17 | 1978-09-26 | E. I. Du Pont De Nemours And Company | Sulfur-substituted isothioureas in silver halide emulsions |
US4351896A (en) * | 1980-12-12 | 1982-09-28 | Eastman Kodak Company | Mesoionic silver halide stabilizer precursor and use in a heat developable and heat stabilizable photographic silver halide material and process |
US4404390A (en) * | 1980-12-12 | 1983-09-13 | Eastman Kodak Company | Mesoionic 1,2,4-triazolium silver halide stabilizer precursors |
US4696763A (en) * | 1984-05-11 | 1987-09-29 | Ciba-Geigy Corporation | Compositions containing heterocyclic corrosion inhibitors |
EP0323146A2 (en) * | 1987-12-29 | 1989-07-05 | Smithkline Beecham Corporation | Dopamine-beta-hydroxylase inhibitors |
US5478721A (en) * | 1995-01-31 | 1995-12-26 | Eastman Kodak Company | Photographic elements containing emulsion stabilizers |
CN115477613A (zh) * | 2022-10-28 | 2022-12-16 | 陕西师范大学 | 一种合成2-氨基咪唑啉类化合物的方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2653447A1 (de) * | 1975-11-26 | 1977-06-08 | Fisons Ltd | Die verwendung von triazoliumverbindungen als schaedlingsbekaempfungsmittel |
US4390538A (en) * | 1980-09-12 | 1983-06-28 | Ciba-Geigy Corporation | Pesticidal triorgano-tin triazines |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB699888A (en) * | 1951-01-26 | 1953-11-18 | Du Pont | Photographic materials and processes |
-
0
- BE BE555210D patent/BE555210A/xx unknown
-
1956
- 1956-02-23 US US567418A patent/US2819965A/en not_active Expired - Lifetime
-
1957
- 1957-02-20 FR FR1173222D patent/FR1173222A/fr not_active Expired
- 1957-02-25 GB GB6176/57A patent/GB859143A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB699888A (en) * | 1951-01-26 | 1953-11-18 | Du Pont | Photographic materials and processes |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2981624A (en) * | 1957-06-05 | 1961-04-25 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsion |
US3042521A (en) * | 1957-12-26 | 1962-07-03 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsion |
US2948615A (en) * | 1958-03-13 | 1960-08-09 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsions |
US2939789A (en) * | 1958-06-06 | 1960-06-07 | Gen Aniline & Film Corp | Fog reduction in photographic silver halide emulsions |
US2919985A (en) * | 1958-08-15 | 1960-01-05 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsions |
US3051570A (en) * | 1958-10-01 | 1962-08-28 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsions |
US3081170A (en) * | 1958-10-06 | 1963-03-12 | Gen Aniline & Film Corp | Fog reduction in photographic silver halide emulsions |
US2952539A (en) * | 1958-10-23 | 1960-09-13 | Gen Aniline & Film Corp | Photographic emulsions and developers stabilized with purine compounds |
US2976152A (en) * | 1958-12-19 | 1961-03-21 | Gen Aniline & Film Corp | Photographic gelatin layers containing triazine hardeners |
US3068239A (en) * | 1959-12-28 | 1962-12-11 | Monsanto Chemicals | Benzothiazole-, benzoxazole- and benzimidazole-2-thioacrylates and process |
US3136689A (en) * | 1959-12-28 | 1964-06-09 | Monsanto Co | Heterocyclic esters effective against micro-organisms |
US3084044A (en) * | 1960-12-09 | 1963-04-02 | Gen Aniline & Film Corp | Nitrogenous heterocyclic carboxyal-kylmercapto polyoxyalkylene ester photographic sensitizer |
US3220839A (en) * | 1961-08-25 | 1965-11-30 | Eastman Kodak Co | Photographic emulsions containing isothiourea derivatives |
US3252799A (en) * | 1962-06-09 | 1966-05-24 | Agfa Ag | Stabilized silver halide emulsions |
US3365294A (en) * | 1963-04-27 | 1968-01-23 | Agfa Ag | Photographic material containing yellow fog-preventing agents |
US3325287A (en) * | 1963-11-26 | 1967-06-13 | Fuji Photo Film Co Ltd | Photographic gelatin hardening composition |
DE2222297A1 (de) * | 1971-05-11 | 1972-11-23 | Agfa Gevaert Ag | Photographisches Silberhalogenidmaterial |
US3896129A (en) * | 1972-03-31 | 1975-07-22 | American Home Prod | (2-pyrimidinylthio) alkanoic acids, esters, amides and hydrazides |
US3901887A (en) * | 1972-03-31 | 1975-08-26 | American Home Prod | (2-pyrimidinylthio) alkanoic acids, esters, amides and hydrazides |
US3940394A (en) * | 1972-03-31 | 1976-02-24 | Santilli Arthur A | 2-pyrimidinylthio)alkanoic acids, esters, amides and hydrazides |
JPS4972735U (US07166745-20070123-C00016.png) * | 1972-10-14 | 1974-06-24 | ||
US4009029A (en) * | 1973-06-05 | 1977-02-22 | Eastman Kodak Company | Cyanoethyl-containing blocked development restrainers |
US4111697A (en) * | 1976-03-29 | 1978-09-05 | Agfa-Gevaert, N. V. | Novel antifogging and/or stabilizing compounds for silver halide photography |
US4116697A (en) * | 1976-12-17 | 1978-09-26 | E. I. Du Pont De Nemours And Company | Sulfur-substituted isothioureas in silver halide emulsions |
US4351896A (en) * | 1980-12-12 | 1982-09-28 | Eastman Kodak Company | Mesoionic silver halide stabilizer precursor and use in a heat developable and heat stabilizable photographic silver halide material and process |
US4404390A (en) * | 1980-12-12 | 1983-09-13 | Eastman Kodak Company | Mesoionic 1,2,4-triazolium silver halide stabilizer precursors |
US4696763A (en) * | 1984-05-11 | 1987-09-29 | Ciba-Geigy Corporation | Compositions containing heterocyclic corrosion inhibitors |
EP0323146A2 (en) * | 1987-12-29 | 1989-07-05 | Smithkline Beecham Corporation | Dopamine-beta-hydroxylase inhibitors |
EP0323146A3 (en) * | 1987-12-29 | 1991-01-30 | Smithkline Beecham Corporation | Dopamine-beta-hydroxylase inhibitors |
US5478721A (en) * | 1995-01-31 | 1995-12-26 | Eastman Kodak Company | Photographic elements containing emulsion stabilizers |
CN115477613A (zh) * | 2022-10-28 | 2022-12-16 | 陕西师范大学 | 一种合成2-氨基咪唑啉类化合物的方法 |
CN115477613B (zh) * | 2022-10-28 | 2024-04-26 | 陕西师范大学 | 一种合成2-氨基咪唑啉类化合物的方法 |
Also Published As
Publication number | Publication date |
---|---|
GB859143A (en) | 1961-01-18 |
BE555210A (US07166745-20070123-C00016.png) | |
FR1173222A (fr) | 1959-02-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2819965A (en) | Carboxymethylmercapto compounds as stabilizers for photographic emulsions | |
US2983611A (en) | Gelatin compositions containing hardeners | |
US2870015A (en) | Stabilized photographic silver halide emulsions | |
US3397987A (en) | Photographic emulsion containing mercapto development anti-foggants | |
US3137578A (en) | Photographic emulsions containing 2-heterocyclic benzimidazole antifoggants | |
US3364028A (en) | Photographic material containing yellow fog-preventing agents | |
US3071465A (en) | Fog reduction in silver halide emulsions by 2h-tetrazolium halides | |
US2981624A (en) | Antifoggants and stabilizers for photographic silver halide emulsion | |
US3266897A (en) | Antifoggant agents for photography | |
US3615617A (en) | Stabilized photographic material with tetrazole thiocarbonic acid ester | |
US3023103A (en) | Antifoggants and stabilizers for photographic silver halide emulsions | |
JPS5943728B2 (ja) | ハロゲン化銀写真材料 | |
US3791830A (en) | Silver halide photographic element containing a reaction product of a heterocyclic mercaptan and a chloroformic acid ester as antifog agent | |
US3161520A (en) | Fog reduction in photographic silver halide emulsions | |
US2887378A (en) | Photographic silver halide emulsions containing thiol compounds | |
US2952539A (en) | Photographic emulsions and developers stabilized with purine compounds | |
US4634660A (en) | Development-processing method for silver halide photographic light-sensitive material | |
US2743181A (en) | Stabilized photographic silver halide emulsions | |
US2852375A (en) | New tetrazaindene compounds and photographic emulsions containing them | |
US4920043A (en) | Method for processing silver halide photographic light-sensitive material | |
US2860985A (en) | Stabilization of photographic silver halide emulsions and means of increasing contrast | |
US3051570A (en) | Antifoggants and stabilizers for photographic silver halide emulsions | |
US3408196A (en) | Sensitization of silver halide emulsion with labile selenium formed in situ | |
DE69126815T2 (de) | Photographische Silberhalogenidmaterialien | |
US2824001A (en) | Stabilized photographic silver halide emulsions |