CA2034850A1 - Infrared sensitive silver halide color photographic elements - Google Patents
Infrared sensitive silver halide color photographic elementsInfo
- Publication number
- CA2034850A1 CA2034850A1 CA002034850A CA2034850A CA2034850A1 CA 2034850 A1 CA2034850 A1 CA 2034850A1 CA 002034850 A CA002034850 A CA 002034850A CA 2034850 A CA2034850 A CA 2034850A CA 2034850 A1 CA2034850 A1 CA 2034850A1
- Authority
- CA
- Canada
- Prior art keywords
- silver halide
- infrared
- group
- sensitized
- photographic element
- 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.)
- Abandoned
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 79
- 239000004332 silver Substances 0.000 title claims abstract description 79
- -1 silver halide Chemical class 0.000 title claims abstract description 75
- 239000000839 emulsion Substances 0.000 claims abstract description 78
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001228 spectrum Methods 0.000 claims abstract description 30
- 150000001875 compounds Chemical group 0.000 claims abstract description 21
- 230000005855 radiation Effects 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 150000004820 halides Chemical class 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004442 acylamino group Chemical group 0.000 claims description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 65
- 239000010410 layer Substances 0.000 abstract description 50
- 230000035945 sensitivity Effects 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 7
- 229910052729 chemical element Inorganic materials 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000003086 colorant Substances 0.000 abstract description 2
- 229940009188 silver Drugs 0.000 description 67
- 238000009740 moulding (composite fabrication) Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 9
- 230000001235 sensitizing effect Effects 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 239000004848 polyfunctional curative Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000000326 densiometry Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000013074 reference sample Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JTADLCMPZGCLCU-UHFFFAOYSA-N 1-[3,5-bis(trifluoromethyl)phenyl]-2h-tetrazole-5-thione Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(N2C(N=NN2)=S)=C1 JTADLCMPZGCLCU-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical class C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 150000002540 isothiocyanates Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 102000005962 receptors Human genes 0.000 description 2
- 108020003175 receptors Proteins 0.000 description 2
- 230000003578 releasing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- MMMJZCONCALLBM-UHFFFAOYSA-N 1-[2-(trifluoromethyl)phenyl]-2h-tetrazole-5-thione Chemical compound FC(F)(F)C1=CC=CC=C1N1C(=S)N=NN1 MMMJZCONCALLBM-UHFFFAOYSA-N 0.000 description 1
- FXOSSGVJGGNASE-UHFFFAOYSA-N 1-isothiocyanato-3,5-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC(N=C=S)=CC(C(F)(F)F)=C1 FXOSSGVJGGNASE-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- LLCOQBODWBFTDD-UHFFFAOYSA-N 1h-triazol-1-ium-4-thiolate Chemical class SC1=CNN=N1 LLCOQBODWBFTDD-UHFFFAOYSA-N 0.000 description 1
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- CDIDGWDGQGVCIB-UHFFFAOYSA-N 3,5-bis(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 CDIDGWDGQGVCIB-UHFFFAOYSA-N 0.000 description 1
- XUEDGYZCOWRRAP-UHFFFAOYSA-N 4-phenyl-3-sulfanyl-2h-tetrazole Chemical compound SN1NN=CN1C1=CC=CC=C1 XUEDGYZCOWRRAP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical class C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 description 1
- 125000004471 alkyl aminosulfonyl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005422 alkyl sulfonamido group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000004891 diazines Chemical class 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical class C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PTFYQSWHBLOXRZ-UHFFFAOYSA-N imidazo[4,5-e]indazole Chemical compound C1=CC2=NC=NC2=C2C=NN=C21 PTFYQSWHBLOXRZ-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- YGNGABUJMXJPIJ-UHFFFAOYSA-N thiatriazole Chemical class C1=NN=NS1 YGNGABUJMXJPIJ-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 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
-
- 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
-
- 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
- G03C1/08—Sensitivity-increasing substances
- G03C1/28—Sensitivity-increasing substances together with supersensitising substances
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- 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
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- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
- G03C5/164—Infra-red processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/145—Infrared
Abstract
Infrared Sensitive Silver Halide Photographic Elements ABSTRACT OF DISCLOSURE
An infrared sensitive silver halide photographic element is disclosed comprising a support and at least one silver halide emulsion layer spectrally sensitized to the infrared portion of the electromagnetic spectrum. In par-ticular, an infrared sensitive color photographic element, capable of providing full color images without exposure to corresponding visible radiation, is disclosed, said ele-ment comprising at least three silver halide emulsion lay-ers on a substrate, each associated with different photo-graphic color image forming materials, such as color cou-plers capable of forming dyes of different colors upon reaction with an oxidized color photographic developer, diffusing dyes, bleachable dyes, or oxidized leuco dyes.
The three emulsion layers are sensitized to three differ-ent portions of the electromagnetic spectrum with at least two layers sensitized to different regions of the infrared region of the electromagnetic spectrum. The infrared sen-sitive element is characterized in that at least one in-frared sensitized emulsion layer is associated with a 1-aryl-5-mercaptotetrazole compound substituted in the aryl group by at least one electron-attracting group.
The infrared sensitive photographic element has high sensitivity to infrared radiation and undergoes less change in sensitivity during storage.
An infrared sensitive silver halide photographic element is disclosed comprising a support and at least one silver halide emulsion layer spectrally sensitized to the infrared portion of the electromagnetic spectrum. In par-ticular, an infrared sensitive color photographic element, capable of providing full color images without exposure to corresponding visible radiation, is disclosed, said ele-ment comprising at least three silver halide emulsion lay-ers on a substrate, each associated with different photo-graphic color image forming materials, such as color cou-plers capable of forming dyes of different colors upon reaction with an oxidized color photographic developer, diffusing dyes, bleachable dyes, or oxidized leuco dyes.
The three emulsion layers are sensitized to three differ-ent portions of the electromagnetic spectrum with at least two layers sensitized to different regions of the infrared region of the electromagnetic spectrum. The infrared sen-sitive element is characterized in that at least one in-frared sensitized emulsion layer is associated with a 1-aryl-5-mercaptotetrazole compound substituted in the aryl group by at least one electron-attracting group.
The infrared sensitive photographic element has high sensitivity to infrared radiation and undergoes less change in sensitivity during storage.
Description
~03485~
Infrared Sensitive Silver Halide PhotoqraPhic Elements FIELD OF THE I~VENTION
This invention relates to silver halide photographic elements sensitive to infrared radiation. In particular, the present invention relates to color photographic ele-ments having at least three silver halide emulsion layers associated with color image providing materials, each emulsion layer being sensitized to a different region of the electromagnetic spectrum and at least two emulsion layers being sensitized to radiation within the infrared region of the electromagnetic spectrum, wherein at least on infrared sensitized emulsion layer is associated with an arylmercaptotetrazole derivative.
BACKGROUND OF THE ART
Dyes which have been capable of sensitizing silver halide emulsions to infrared regions of the electromagnet-ic spectrum have been known for many years. Merocyanine dyes and cyanine dyes, particularly those with longer bridging groups between cyclic moieties, have been used for many years to sensitize silver halide to the infrared.
US Pat. Nos. 3,619,154, 3,682,630, 2,895,955, 3,482,978, 3,758,461 and 2,734,900; and GB Pat. Nos. 1,192,234 and 1,188,784 disclose well-known classes of dyes which sensi-tize silver halide to portions of the infrared region of the electromagnetic spectrum. US Pat. No. 4,362,800 dis-closes dyes to sensitize inorganic photoconductors to the infrared, and these dyes are also effective sensitizers for silver halide.
With the advent of lasers, and particularly solid state laser diodes emitting in the infrared region of the electromagnetic spectrum (e.g., 780 to 1500nm), the inter-est in infrared sensitization has greatly increased. Many - ~ ~ 2034850 different processes and articles useful with laser diodes have been proposed. US Pat. No. 4,011,083 discloses photo-graphic elements having a defined pAg, infrared spectral sensitizing methine dyes of defined polarographic cathodic halfwave potential and silver complexing azaindenes, said elements having higher speed in ~he spectrally sensitized region. US Pat. No. 4,416,522 proposes daylight photoplotting apparatus for the infrared exposure of film.
This patent also generally proposes a film comprising three emulsion layers sensitized to different portions of non-visible portions of the electromagnetic spectrum, in-cluding the infrared. The film description is quite gener-al and the concentration of imagewise exposure on each layer appears to be dependent upon filtering of the radia-tion by the apparatus prior to its striking the film sur-face. US Pat. No. 4,619,892 describes a photographic ele-ment capable of providing full color images without e~po-sure to corresponding visible radiation, said element com-prising at least three silver halide emulsion layers on a substrate, each associated with different photographic color image forming materials and sensitized to three different portions of the electromagnetic spectrum with at least two layers sensitized to different regions of the infrared region of the electromagnetic spectrum.
It is also known that the addition of specific organ-ic compounds to a silver halide photographic material in addition to the spectrally sensitizing dyes can increase the spectrally sensitized speed of the emulsion by more than one order of magnitude. This is known as a super-sensitizing effect. As organic compounds for supersensi-tization of infrared sensitized silver halide emulsions which are conventionally known, there are illustrated, for example, triazine derivatives described in US Pat. Nos.
Infrared Sensitive Silver Halide PhotoqraPhic Elements FIELD OF THE I~VENTION
This invention relates to silver halide photographic elements sensitive to infrared radiation. In particular, the present invention relates to color photographic ele-ments having at least three silver halide emulsion layers associated with color image providing materials, each emulsion layer being sensitized to a different region of the electromagnetic spectrum and at least two emulsion layers being sensitized to radiation within the infrared region of the electromagnetic spectrum, wherein at least on infrared sensitized emulsion layer is associated with an arylmercaptotetrazole derivative.
BACKGROUND OF THE ART
Dyes which have been capable of sensitizing silver halide emulsions to infrared regions of the electromagnet-ic spectrum have been known for many years. Merocyanine dyes and cyanine dyes, particularly those with longer bridging groups between cyclic moieties, have been used for many years to sensitize silver halide to the infrared.
US Pat. Nos. 3,619,154, 3,682,630, 2,895,955, 3,482,978, 3,758,461 and 2,734,900; and GB Pat. Nos. 1,192,234 and 1,188,784 disclose well-known classes of dyes which sensi-tize silver halide to portions of the infrared region of the electromagnetic spectrum. US Pat. No. 4,362,800 dis-closes dyes to sensitize inorganic photoconductors to the infrared, and these dyes are also effective sensitizers for silver halide.
With the advent of lasers, and particularly solid state laser diodes emitting in the infrared region of the electromagnetic spectrum (e.g., 780 to 1500nm), the inter-est in infrared sensitization has greatly increased. Many - ~ ~ 2034850 different processes and articles useful with laser diodes have been proposed. US Pat. No. 4,011,083 discloses photo-graphic elements having a defined pAg, infrared spectral sensitizing methine dyes of defined polarographic cathodic halfwave potential and silver complexing azaindenes, said elements having higher speed in ~he spectrally sensitized region. US Pat. No. 4,416,522 proposes daylight photoplotting apparatus for the infrared exposure of film.
This patent also generally proposes a film comprising three emulsion layers sensitized to different portions of non-visible portions of the electromagnetic spectrum, in-cluding the infrared. The film description is quite gener-al and the concentration of imagewise exposure on each layer appears to be dependent upon filtering of the radia-tion by the apparatus prior to its striking the film sur-face. US Pat. No. 4,619,892 describes a photographic ele-ment capable of providing full color images without e~po-sure to corresponding visible radiation, said element com-prising at least three silver halide emulsion layers on a substrate, each associated with different photographic color image forming materials and sensitized to three different portions of the electromagnetic spectrum with at least two layers sensitized to different regions of the infrared region of the electromagnetic spectrum.
It is also known that the addition of specific organ-ic compounds to a silver halide photographic material in addition to the spectrally sensitizing dyes can increase the spectrally sensitized speed of the emulsion by more than one order of magnitude. This is known as a super-sensitizing effect. As organic compounds for supersensi-tization of infrared sensitized silver halide emulsions which are conventionally known, there are illustrated, for example, triazine derivatives described in US Pat. Nos.
2,875,058 and 3,695,888, mercapto compounds described in US Pat. No. 3,457,078, thiourea compounds described in US
Pat. No. 3,458,318, pyrimidine derivatives described in US
Pat. No. 3,615,632, azaindene compounds described in US
_ 3 - Z0~4850 Pat. No. 4,011,083, triaryl compounds described in US Pat.
No. 4,578,347, thiazolium and oxazolium salts described in US Pat. No. 4,596,767, combinations of supersensitizers described in US Pat. No. 4,603,104 and thiatriazoles described in US Pat. No. 4,780,404.
Photographic elements comprising silver halide emul-sion layers sensitized to infrared regions of the electro-magnetic spectrum, in particular color photographic ele-ments associated with photographic color image forming materials, are generally liable to undergo changes in sen-sitivity if stored under different conditions of humidity and temperature. Such change in photographic sensitivity is a critical problem in the use of infrared sensitized photographic materials. It is well known that commercial-ly available photographic materials having sensitivity in the infrared region are unstable in sensitivity and re-quire special caution for preservation thereof, such as storage in a refrigerator. Conventionally known stabiliz-ers such as 1-phenyl-5-mercaptotetrazole are not effective for improving stability of infrared sensitized photograph-ic materials. Therefore, a need exists to develop a tech-nique wich specifically improves the stability on storage of infrared sensitized emulsions.
Mercaptotetrazoles are generally disclosed in US Pat.
Nos. 3,Z66,897 (carboxysubstituted mercapto tetrazoles for use as antifoggants in silver halide emulsions) and 3,397,987 (heterocyclic nitrogen compounds containing a mercapto function for use as development fog inhibitors in silver halide emulsions comprising unfogged surface latent image grains and fogged internal image silver halide grains).
US Pat. No. 3,637,393 describes the use of mer-captotetrazoles in combination with certain hydroquinone compounds to reduce fog and increase speed in silver halide color photographic emulsions.
US Pat. No. 3,457,078 describes the use of mercapto substituted oxazine, oxazole, thiazole, thidiazole, - ~ - 20;~4850 imidazole, or tetrazole, the mercapto substituted compound further containing an electronegative substituent, as supersensitizers and antifoggants in combination with cer-tain cyanine dyes. 1-Phenyl-2-mercaptotetrazole is a suit-able substance disclosed in said patent.
Japanese Pat. Appln. No. J0 1013-539 describes the combined use of mercaptotriazole derivatives and mercaptotetrazole derivatives as supersensitizers in in-frared sensitive silver halide materials.
US Pat. No. 4,603,104 describes the combined use of arylmercaptotetrazoles and others supersensitizers tb in-crease the speed of spectrally sensitized silver halide photographic emulsions.
SUMMARY OF THE INVENTION
An infrared sensitive photographic element is dis-closed which comprises at least one silver halide emulsion layer spectrally sensitized to the infrared portion of the electromagnetic spectrum. In particular, the element com-prises at least three silver halide emulsion layers on a substrate, each associated with different photographic color image forming materials, such as color couplers ca-pable of forming dyes of different colors upon reaction with an o~idized color photographic developer, diffusing dyes, bleachable dyes, or o~idized leuco dyes. The three emulsion layers are sensitized to three different portions of the electromagnetic spectrum with at least two ~ayers sensitized to different regions of the infrared region of the electromagnetic spectrum. The element is characterized in that at least one infrared sensitized emulsion layer is associated with an 1-aryl-5-mercaptotetrazole compound substituted in the aryl group by at least one electron-attracting group.
The infrared sensitive photographic element has high sensitivity to infrared radiation and undergoes less change in sensitivity during storage.
;2034850 DETAILED DESCRIPTION OF THE INVENTION
An infrared sensitive photographic element is herein described which element comprises a support and one or more silver halide emulsion layers, at least one silver halide emulsion layer being spectrally sensitized to the infrared portion of the electromagnetic spectrum. In par-ticular, an infrared sensitive color photographic element is herein described which element is capable of providing a full color image or three color images with exposure of at least two silver halide emulsion layers to radiation outside the visible region of the electromagnetic spec-trum, which element comprises a substrate, and on one side of said substrate at least three silver halide emulsion layers, each of said silver halide emulsion layers being associated with means for forming a single color image of a different color dye, said three emulsion layers being sensitized to three different portions of the electromag-netic spectrum with at least two layers sensitized to dif-ferent regions of the infrared region of the electromag-netic spectrum. The element is characterized in that at least one infrared sensitized emulsion layer is associated with an 1-aryl-5-mercaptotetrazole compound substituted in the-aryl group by at least one electron-attracting group.
Preferably, the compounds of the present invention are represented by the structural formula (I) N N
N~ ~C-SH
Ar wherein Ar is an aryl group bearing at least one electron-attracting group. More preferably, the aryl group is a phenyl group and the electron-attracting groups are selected from the group consisting of nitro, cyano, - 6 - 2034~50 fluoroalkyl, halogen (preferably, chlorine or bromine), carbamoyl (preferably, a C1 to C4 straight or branched alkylaminocarbonyl or an unsubstituted or substituted phenylaminocarbonyl group), sulfamoyl (preferably, a Cl to C4 straight or branched alkylaminosulfonyl or an unsubstituted or substituted phenylaminosulfonyl group), acylamino (preferably, a C1 to C4 straight or branched alkylcarbonamido or an unsubstituted or substituted phen-ylcarbonamido group), sulfonamido (preferably, a C1 to C4 straight or branched alkylsulfonamido or an unsubstituted or substituted phenylsulfonamido group) and acyl (prefera-bly, a C1 to C~ straight or branched alkylcarbonyl or an unsubstituted or substituted phenylcarbonyl group).
Still more preferably, the compounds of the present invention are represented by the structural formula (I) wherein Ar is a phenyl group bearing one or more Cl to C~
straight or branched fluoroalkyl groups, wherein the alkyl group has at least one fluorine atom per carbon atom, preferably at least 1.5 fluorine atoms per carbon atom, more preferably all hydrogen atoms substituted with fluo-rine atoms.
When the term "group" is used in this invention to describe a chemical compound or substituent, the described chemi~al material includes the basic group and that group with conventional substitution. Where the term "moiety" is used to describe a chemical compound or substituent, only an unsubstituted chemical material is intended to be in-cluded. For example, "alkyl group" includes not only such alkyl moieties as methyl, ethyl, octyl, stearyl, etc., but also such moieties bearing substituent groups such as halogen, cyano, hydroxyl, nitro, amine, carboxylate, etc.
On the other hand, "alkyl moiety" includes only methyl, ethyl, octyl, stearyl, cyclohexyl, etc.
Specific examples of aryl groups substituted with one or more electron-attracting groups are, for example, a 4-nitrophenyl group, 2-nitro-4-N,N-dimethylsulfamoylphenyl group, 2-N,N-dimethylsulfamoyl-4-nitrophenyl group, , ~ 7 ~ 203~850 2-cyano-4-methylsulfonylphenyl group, 2,4-dinitrophenyl group, 2,4,6-tricyanophenyl group, 2-nitro-4-N,N-dimethyl-carbamoylphenyl group, 2,4-dimethanesulfonylphenyl group, 3,5-dinitrophenyl group, 2-chloro-4-nitro-5-methylphenyl group, 2-nitro-3,5-dimethyl-4-tetradecylsulfonylphenyl group, 2,4-dinitronaphthyl group, 2-ethylcarbamoyl-4-nitrophenyl group, 3,5-bistrifluoromethylphenyl group, 2,3,4,5,6-pentafluorophenyl group, 3-acetamidophenyl group, 2-acetyl-4-nitrophenyl group, 2,4-diacetylphenyl group, 2-nitro-4-trifluoromethyl phenyl group, 4-ethoxy-carbonyl phenyl group.
The compounds of the present invention represented by the general formula (I) may be added in any effective sta-bilizing amount to the photographic emulsion. The concen-tration of said compounds can vary significantly in photo-graphic emulsions. A generally useful range would be from 0.008 to 0.28 g per mol of silver. A more preferred range would be from 0.015 to 0.150 g per mol of silver. The com-pounds of the present invention can be directly dispersed in the photographic emulsion, or may be dissolved in a suitable solvent (e.g., water, methyl alcohol, ethyl alco-hol, propanol, methyl cellosolve, acetone, etc.) or in a mixture of these solvents and added as a solution to the emulsion. In addition, said compounds can be added to the emulsion as a solution or as a colloid dispersion accord-ing to the processes for adding sensitizing dyes, as known to those skilled in the art.
Any spectral sensitizing dye known to sensitize sil-ver halide emulsions to infrared portion of the electro-magnetic spectrum may be used in the practice of the present invention with the stabilizer compounds of the present invention. The infrared portion of the electromag-netic spectrum is given various ranges, but is generally considered to be between 750 and 1500 nm which overlaps a small portion of the visible regions of the electromagnet-ic spectrum (e.g., about 750-780 nm). Useful dyes for this - 8 - Z 0 3 4 85 ~
purpose tend to be merocyanines, cyanines and especially tricarbocyanines. Such dye sensitizers for the infrared are described for example in US Pat. Nos. 3,457,078, 3,619,154, 3,682,630, 3,690,891, 3,695,888, 4,030,932 and 4,367,800. The preferred classes of dyes are the tricarbocyanines such as 3,3'-dialkylthiatricarbocyanines, thiatricarbocyanines (especially with rigidized chains), selenotricarbocyanines, and enamine tricarbocyanines.
Preferred classes of dyes according to the present invention are represented by the following general formula (II) or (III):
R2 ~3 / C (II) Ro-N-(CH=CH)n-C=CH-C=CH-C=CH-CH=CH-C(=CH-CH)~=N+Rl Z1 1 14 _ Z2 (III) Ro~N~( CH=CH)n-C=CH-C=CH-C=CH-CH=CH-C(=CH-CH)~=N~R
X
wherein:
Ro and R1 can be a substituted alkyl group or a nonsubstituted alkylgroup having from 1 to 8 carbon atoms such as , for example, methyl, ethyl, propyl, butyl, amyl, benzyl, octyl, carboxymethyl, carboxyethyl, sulfopropyl, carboxypropyl, carboxybutyl, sulfoethyl,- sulfoisopropyl and sulfobutyl groups;
X-is any acid anion such as, for example, chloride, bromide, iodide, tri-iodide, perchlorate, sulfamate, thio-cyanate, p-toluenesulfonate and benzenesulfonate;
Z1 and Z2 are independently the non-metallic atoms necessary to complete an aromatic heterocyclic nucleus chosen within those of the thiazole series, benzothiazole series, (i,2-d)-naphthothiazole series, (2,1-d)-naphtho-thiazole series, oxazole series, benzoxazole series, - 9- Z0~4850 selenazole series, benzoselenazole series, (1,2-d)-naphthoselenazole series, ~2,1-d)-naphthoselenazole series, thiazoline series, 4-quinoline series, 2-pyridine series, 4-pyridine series, 3,3'-dialkyl-indolenine series (wherein alkyl has a meaning known to those skilled in the art including alkyl groups having 1 to 12 carbon atoms), imidazole series and benzimidazole series.
More particularly and preferably, the present inven-tion refers to dyes of the type above indicated in which both heterocyclic nuclei are of the benzothiazole series.
R2 and R3 each represent a hydrogen atom, or an alkyl goup having 1 to 5 carbon atoms such as a methyl group or an ethyl group; R~ represents a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 5 car-bon atoms, an unsubstituted or substituted aryl group, an acyloxy group shown by -C-O-Rs wherein Rs represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a su~stituted phenyl group.
The infrared sensitizing dyes of the present inven-tion are incorporated in the silver halide photographic emulsion in a content of 5xlO-7mol to 5xlO~3mol, prefer-ably lxlO- 6 mol to lxlO-3mol, more preferably 2~10- 6 mol to 5xlO-~mol, per mol of silver.
The infrared sensitizing dyes to be used in the present invention can be directly dispersed in the emul-sion. Alternatively, they may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixture thereof to add them to the emulsion as a solution. Pro-cesses for adding the infrared sensitizing dyes to the photographic emulsion are described, for example, in US
Pat. Nos. 3,469,987, 3,676,147, 3,822,135, 4,199,360, and in US Pat. Nos. 2,912,343, 3,342,605, 2,996,287 and 3,429,83S; The aforesaid infrared sensiti~ing dyes may be - 10- ~03485(~
uniformly dispersed in the silver halide emulsion before coating on a suitable support~ Of course, this dispersing procedure may be conducted in any step of preparing the silver halide emulsion.
The ratio (by wei~ht) of the amount of the infrared sensitizing dye to that of the compound represented by the general formula (I) is advantageously 1/1 to 1/30, partic-ularly advantageously 1/2 to lt50.
Infrared sensitive silver halide photographic ele-ments for use in the present invention are preferably those described in US Pat. No. 4,619,892, which is incor-porated herein by reference. More preferably, the infrared sensitive silver halide color photographic elements for use in the present invention are those having all of the silver halide emulsion layers sensitized to different in-frared regions of the electromagnetic spectrum. The order of these layers respect to the support, the difference in emulsion sensitivity among the layers and the sensitivity, contrast and D-max of each layer are preferably those de-scribed in said US Pat. No. 4,619,892.
Any of the various types of photographic silver halide emulsions may be used in the practice of the present invention. Silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and mixture thereof may be used, for example, dispersed in a hydrophilic colloid or carrier.
Any configuration of grains, cubic, orthorombic, hexago-nal, epitaxial, or tabular (high aspect ratio) grains may be used. The colloid may be partially hardened or fully hardened by any of the variously known photographic hard-eners. Such hardeners are free aldehydes, aldehyde releas-ing comounds, triazines and diazines, aziridines, vinylsulfones, carbodiimides, and the like may be used, as described, for example, in US Pat. Nos. 3,232,764, 2,870,013, 3,819,608, 3,325,287, 3,992,366, 3,271,175 and 3,490,911;
The silver halide photographic elements can be used ;~0348S0 to form dye images therein through the selective formation of dyes. The photographic elements described above for forming silver images can be used to form dye images by employing developers containing dye image formers, such as color couplers, as described, for example, in US Pat. Nos.
3,111,864, 3,002,836, 2,271,238, 2,Z36,598, 2,950,970, 2,592,243, 2,3~3,703, 2,376,380, 2,369,489, 2,899,306, 3,152,896, 2,115,394, 2,252,718, 2,108,602, and 3,547,650.
In this form the developer contains a color developing agent (e.g., a primary aromatic amine which in its oxi-dized form is capable of reacting with the coupler to form the image dye). Also, instant self-developing diffusion transfer film can be used as well as photothermographic color film or paper using silver halide in catalytic pro~-imity to reducable silver sources and leuco dyes.
The dye-forming couplers can be incorporated in the photographic elements, as illustrated by Schneider et al., Die Chemie, Vol. 57, 1944, p.113, and in US Pat. Nos.
2,304,940, Z,269,158, 2,322,027, 2,376,679, 2,801,171, 2,748,141, 2,772,163, 2,835,579, 2,533,514, 2,353,754, 3,409,435 and Chen, Research Disclosure, Vol. 159, July 1977, Item 15930. The dye-forming couplers can be incorpo-rated in different amounts to achieve differing photo-graphic effects. For example, GB Pat. No. 923,045 and US
Pat. No. 3,843,369 teach limiting the concentration of coupler in relation to the silver coverage to less than normally employed amounts in faster and intermediate speed emulsion layers.
The dye-forming couplers are commonly chosen to form subtractive primary (i.e., yellow, magenta and cyan) image dyes and are nondiffusible, colorless couplers, such as two and four equivalent couplers of the open chain keto-methylene, pyrazolone, pyrazolotriazole, pyrazolobenz-imidazole, phenol and naphthol type hydrophobically bal-lasted for incorporation in high-boiling organic (coupler) solvents: Such couplers are illustrated in US Pat. Nos.
2,423,730, 2,772,162, 2,895,826, 2,710,803, 2,407,207, 3,737,316, 2,367,531, 2,772,161, 2,600,788, 3,006,759, 3,214,437, 3,253,924, 2,875,057, 2,908,573, 3,043,892, 2,474,293, 2,407,210, 3,06~,653, 3,265,506, 3,384,657, 2,343,703, 3,127,269, 2,865,748, 2,933,391, 2,865,751, 3,725,067, 3,758,308, 3,779,763, 3,785,829, 3,762,921, 3,983,608, 3,311,467, 3,408,194, 3,458,315, 3,4~7,928, 3,476,563, 3,419,390, 3,419,391, 3,519,429, 3,222,176, 3,227,550, in GB Pat. Nos. 969,921, 1,241,069, 1,011,940, 975,928, 1,111,554, 1,248,g24, and in CA Pat. No. 726,651.
Dye-forming couplers of differing reaction rates in single or separate layers can be employed to achieve desired ef-fects for specific photographic applications.
The dye-forming couplers upon coupling can release photographically useful fragments, such as development inhibitors or accelerators, bleach accelerators, develop-ing agents, silver halide solvents, toners, hardeners, fogging agents, antifoggants, competing couplers, chemical or spectral sensitizers and desensitizers. Development inhibitor-releasing (DIR) couplers are illustrated in US
Pat. Nos. 3,148,062, 3,227,554, 3,733,201, 3,617,291, 3,703,375, 3,61~,506, 3,265,506, 3,620,745, 3,632,345, 3,869,Z91, 3,642,485, 3,770,436, 3,808,945, and in GB Pat.
Nos. 1,201,110 and 1,236,767. Dye-forming couplers and nondye-forming compounds which upon coupling release a variety of photographically useful groups are described in US Pat. No. 4,248,962. DIR compounds which do not form dye upon reaction with oxidized color developing agents can be employed, as illustrated in US Pat. Nos. 3,928,041, 3,958,993, 3,961,959, 4,049,455, 4,052,213 and in German OLS Nos. 2,529,350, 2,448,063 and 2,610,546. DIR compounds with oxidatively cleave can be employed, as illustrated in US Pat. Nos. 3,379,529, 3,043,690, 3,364,022, 3,297,445 and 3,287,129. Silver halide emulsions which are relative-ly light insensitive, such as Lipmann emulsions, having been used as interlayers or overcoat layers to prevent or control t~e migration of development inhibitor fragments - 13 - 203~ 850 as described in US Pat. No. 3,892,572.
The photographic elements can incorporate colored dye-forming couplers, such as those employed to form inte-gral masks for negative color images, as illustrated in US
Pat. Nos. 2,449,966, 2,521,908, 3,034,892, 3,476,563, 3,519,429, 2,543,691, 3,028,238, 3,061,432, and/or compet-ing couplers, as illustrated in US Pat. Nos. 3,876,428, 3,580,722, 2,998,314, 2,808,329, 2,742,832 and 2,689,793.
As previously noted, the color provided in the image produced by exposure of each of the dif~erently sensitized silver halide emulsion layers does not have to be produced by color coupler reaction with oxidized color developers.
A number of other color image forming mechanisms well known in the art can also be used. Amongst the commercial-ly available color image forming mechanisms are the diffu-sion transfer of dyes, dye-bleaching, and leuco dye oxi-dation. Each of these procedures is used in commercial products, is well understood by the ordinary skilled pho-tographic artisan, and is used with silver halide emul-sions. Multicolor elements using these different technolo-gies are also commercially available. Converting the ex-isting commercially available systems to the practice of the present invention could be done by routine redesign of the sensitometric parameters of the system and/or the ad-dition of intermediate filter layers as described in US
Pat. No. 4,519,892. For example, in a conventional instant color dye-diffusion transfer element, the sensitivity of the various layers and/or the arrangement of filter layers between the silver halide emulsion layers would be direct-ed by the teachings of the above US patent, the element otherwise remaining the same. This would be true with ei-ther negative-acting or positive-acting silver halide emulsions in the element. The only major, and fairly ap-parent, consideration that must be given to such construc-tion is to insure that the placement of any filter layers does not prevent transfer of the diffusion dye to a recep-tor layer within the element. Using a filter which is not , .
a barrier layer between the receptor layer and the dye-containing layer is the simplest way to address that consideration. Such a layer should not prevent migration of the diffusion dye across the filter layer.
These types of imaging systems are well knawn in the art. Detailed discussions of various dye transfer, diffu-sion processes may be found for example in "A fundamental-ly New Imaging Technology for Instant Photography", W.T.
Harison, Jr., Photographic Science and Engineering, Vol.
20, No. 4, July~August 1976, and Neblette's Handbook of photography and Reprography, Materials, Processes and-Sys-tems, 7th Edition, John. M. Stunge, van Nostrand Reinhold Company, N.Y., 1977, pp. 324-330 and 126. Detailed dis-cussion of dye-bleach color imaging systems are found for example in The Reproduction of Colour, 3rd Ed., R.W.G.
Hunt, Fountain Press, London, England, 1975, pp.325-330;
and The Theory of the Photographic Process, 4th Ed., Mees and ~ames, Macmillan Publishing Co., Inc., N.Y., 1977, pp.
363-366. Pages 366-372 of Mees and James, supra, also dis-cuss dye-transfer processes in great detail. Leuco dye oxidation in silver halide systems are disclosed in such literature as US Pat. Nos. 4,460,681, 4,374,821, and 4,021,240. Diffusion photothermographic color image form-ing systems such as those disclosed in GB Pat. Appln. No.
3,100,458 are also useful in the practice of the present invention.
The photographic elements can include image dye sta-bilizers. Such image dye stabilizers are illustrated in US
Pat. Nos. 3,432,300, 3,698,909, 3,574,627, 3,573,050, 3,764,337, and 4,042,394 and in GB Pat. No. 1,326,889.
Filter dyes can be included in the photographic ele-ments. Said dyes must be selected on the basis of their radiation filtering characteristics to insure that they filter the appropriate wavelengths. Filter dyes and their methods of incorporation into the photographic elements are well-documented in the literature such as US Pat. Nos.
4,440,852, 3,671,648, 3,423,207, and 2,895,955, GB Pat.
.
- 15 - 203~85~
No. 485,624, and Research Disclosure, Vol. 176, December 1978, Item 17643. Filter dyes can be used in the practice of the present invention to provide room-light handleability to the elemen~s. Dyes which will not allow tran~mission of radiation having wavelengths shorter than the shortest wavelength to which one of the emulsion lay-ers has been sensitized can be used in a layer above one or more (preferably all) of the emulsion layers. The cut-off filter dye preferably does not transmit light more than approximately 50 nm less than the shortest wavelength to which any of the emulsion layers have been sensitized.
Filter dyes should also be provided with non-fugitive (i.e., non-migratory) characteristics and should be decolorizable (by bleaching in developer or heat, for ex-ample) or leachable ~e.g., removed by solvent action of any baths).
Other conventional photographic addenda such as coat-ing aids, antistatic agents, acutance dyes, antihalation dyes and layers, antifoggants, latent image stabilizers, antikinking agents, high intensity reciprocity failure reducers, and the like may also be present.
The following examples illustrate a general synthetic procedure which may be used in the preparation of 1-aryl-5-mercaptophenyltetrazole derivatives and non-limiting examples of preferred embodiments of the present inven-tion.
Preparation of 1-(3,5-bistrifluoromethylphenyl)-5-mer-captotetrazole a) 0.052 Mol of thiophosgene were mixed with 60 ml of water and were stirred for 15 minutes. 0.040 Mol of 3,5-bistrifluoromethylaniline were dropped with 30 ml chloroform, and the mixture was stirred for 2 hours at 15C. The organic solution was washed with HCl 2M, dried and the solvent was removed under vacuum to obtain 3,5-bistrifluoromethylphenylisothiocyanate as a yel~ow-red oil, that was used as crude product.
b) 0.040 Mol of the isothiocyanate above and 0.060 mol sodium azide were added to 100 ml of water and re-fluxed for 7 hours. The mi~ture was cooled, filtered, washed twice with ethyl ether to separate the unreacted isothiocyanate, then the solution pH was adjusted to 2.5.
The solid ma~erial which formed was filtered and recrystallized from carbon tetrachloride. Analytical data (IR, NMR, elemental analysis) confirmed the chemical structure.
A photographic emulsion was prepared by precipitation of AgCl and c~nversion to AgBr to provide an emulsion with 85% bromide and 15% chloride with an average grain size of 0.4 micrometers. The emulsion was chemically digested with sodium thiosulfate, added with a dispersion of the magenta dye forming coupler A in a water-insoluble high boiling organic solvent to have a coupler amount of 240.95 g per mol of sil~er, with 1-phenyl-5-mercaptotetrazole as super-sensitizer and stabilizer in a quantity of 127 micromol per mol of silver and sensitized to the 820 nm region of the spectrum with dye B in the quantity of 93xlO- 6 mol per mol of silver. This emulsion, added with conventional surfactants and hardeners, was coated onto a paper support so that the coating silver and the magenta dye forming coupler weights are 0.56 g/m~ and 1.24 g/mZ, respectively (Reference film 1).
Following the procedure described for film 1, films 2 and 3 according to this invention were prepared on substi-tution of 1-phenyl-5-mercaptotetrazole with 36 micromol and 142 micromol per mole of silver, respectively, of 1-(3,5-bistrifluoromethylphenyl)-5-mercaptotetrazole.
Samples of the films were stored for 24 hours to 21%, 50~ and 80%, respectively, relative humidity, then each .
sample was sealed in a sealed bag and stored for three days at 33 C. Each of the film samples was e~posed through an optical wedge using an infrared sensitometer. After e~posure, these samples were processed in a standard Kodak ~P-2 processing color chemistry with conditions similar to those stated in US Pat. No. 4,3~6,873.
After processing, status D densitometry was measured.
Table 1 reports the variations of sensitivity versus the-reference sample stored at 50~ relative humidity (S) and the change in sensitivity amon~ samples stored at 21% and 50% relative humidity (dS$) and among samples stored at 21~ and 50% relative humidity (dSz). The values of sensi-tivity are e~pressed in log E units necessary to have an optical density of 1Ø
Table 1 _________________________________________________________ Film S dS1 dSz _________________________________________________________ 1 1,00 (ref.) +0,10 -0,08 2 -0,01 +0,02 -0,03 3 +0,28 +0,02 -0,01 _________________________________________________________ Coupler A:
O~ O= ~ -CH=CH-C16H33 Cl~ ~ ,Cl Cl - 18 - 203~50 Dye B:
H3C ~ ~CH3 1~ + C-CH=C C-CH=CH-CH=C~) H3 C ~ \ N~ N
A photographic emulsion was prepared by precipitation of AgCl and conversion to AgBr to provide an emulsion with 85% bromide and 15~ chloride with an average grain size of 0.9 micrometers. The emulsion was chemically digested with sodium thiosulfate, added with a dispersion of the cyan dye forming coupler C in a water-insoluble high boiling organic solvent to have a coupler amount of 164.68 g per mol of silver, with 1-phenyl-5-mercaptotetrazole as supersensitizer and stabilizer in a quantity of 5~
micromol per mol of silver and sensitized to the 895 nm region of the spectrum with dye D in the quantity of 45.5xlO- 6 mol per mol of silver. This emulsion, added with conventional surfactants and hardeners, was coated onto a paper support so that the coating silver and the cyan dye forming coupler weights are 0.42 g/m2 and 0.64 g/mZ, re-spectively (Reference film 1).
Following the procedure described for film 1, films 2 and 3 according to this invention were prepared on substi-tution of 1-phenyl-5-mercaptotetrazole with 439 micromol and 8~9 micromol per mole of silver, respectively, of 1-(3,5-bistrifluoromethylphenyl)-5-mercaptotetrazole.
Samples of the films were stored for 24 hours to 21~, 50~ and 80% relative humidity, respectively, then each sample was sealed in a sealed bag and stored for three days at 33~C.
Eacn of the film samples was exposed through an opti-cal wedge using an infrared sensitometer. After exposure, - 19 - 2034~350 these samples were processed in a standard Xodak EP-2 pro-cessing color chemistry with conditions similar to those stated in US Pat. No. 4,346,873.
After processing, status D densitometry was measured.
Table 2 reports the variations of sensitivity versus the reference sample stored at 50% relative humidity (S) and the change in sensitivity among samples stored at 21% and 50% relative humidity- (dSl) and among samples stored at 21% and 50% relative humidity (dS2). The values of sensi-tivity are e~pressed in log E units necessary to have an optical density of 1Ø
Table 2 _________________________________________________________ Film S dS1 dS2 _________________________________________________________ 1 1,00 (ref.) +0,10 -0,38 2 -0,17 0,00 -0,04 3 -0,0~ 0,00 0,00 _________________________________________________________ Coupler C:
OH O H1lCs Cl ~ NH-C-CH-O ~ CsH
H3C ~ C2Hs Cl -Dye D:
~Cl Cl .' ~ ~ ' HsC2-N ~ CH=CH-CH=CH-CH~ ~ N-C2Hs I-E~AMPLE 4 A photographic emulsion was prepared by precipitation of AgCl and conversion to AgBr to provide an emulsion with 85~ bromide and 15% chloride with an average grain size of 0.9 micrometers. The emulsion was chemically digested with sodium thiosulfate, added with a dispersion of the yellow dye forming coupler E in a water-insoluble high boiling organic solvent to have a coupler amount of 157.95 g per mol of silver, with 1-phenyl-5-mercaptotetrazole as super-sensitizer and stabilizer in a quantity of 10 micromol per mol of silver and sensitized to the 760 nm region of the spectrum with dye F in the quantity of 258.4xlO- 6 mol per mol of silver. This emulsion, added with conventional surfactants and hardeners, was coated onto a paper support so that the coating silver and the yellow dye forming cou-pler weights are 0.56 g/m2 and 0.84 g/m2, respectively (Reference film 1).
Following the procedure described for film 1, films 2 and 3 according to this invention were prepared on substi-tution of 1-phenyl-5-mercaptotetrazole with 289 micromol and 578 micromol per mole of silver, respectively, of 1-(3,5-bistrifluoromethylphenyl)-5-mercaptotetrazole.
Samples of the films were stored for 24 hours to 21%, 50~ and 80% relative humidity, respectively, then each sample was sealed in a sealed bag and stored for three days at 33 C.
Each of the film samples was exposed through an opti-cal wedge using an infrared sensitometer. After exposure, these samples were processed in a standard Kodak EP-2 pro-cessing color chemistry with conditions similar to those stated in US Pat. No. 4,346,873.
After processing, status D densitometry was measured.
Table 3 reports the variations of sensitivity versus the reference sample stored at 50~ relative humidity (S) and the change in sensitivity among samples stored at 21~ and 50~ relative humidity (dS1) and among samples stored at ' .
, - 2.~ -21~ and 50% relative humidity (dS2). The values of sensi-tivity are expressed in log E units necessarY to have an optical density of 1Ø
Table 3 _________________________________________________________ Film S dSl dS2 ________________________________________________._________ 1 1,00 (ref.) +0,04 -0,30 2 -0,03 ~0,04 -0,19 3 +0,01 +0,02 -0,13 Coupler E:
CH3 Cl CH3-C-CO - CH-CO-NH- ~ Hl1Cs HC N NH-CO-(CH2)3-O ~ CsH
Il 11 N - C
l \
N O
Dye F:
f2Hs ~-CH=CH-CH=CH-CH ~ I-A phQtographic emulsion was prepared by precipitation of AgCl and conversion to AgBr to provide an e~ulsion with 203~185(~
85~ bromide and 15% chloride with an average grain size of 0.4 micrometers. The emulsion was chemically digested with sodium thiosulfate, added with a dispersion of the magenta dye forming coupler A of Example 1 in a water-insoluble high boiling organic solvent to have a coupler amount of 240.95 g per mol of silver, with 1-phenyl-5-mercaPto-tetrazole as supersensitizer and stabilizer in a quantity of 127 micromol per mol of silver and sensitized to the 820 nm region of the spectrum with dye B of Example 1 in the quantity of 93xlO- 6 mol per mol of silver. This emul-sion, added with conventional surfactants and hardeners,was coated onto a polyester support so that the coating silver and the magenta dye forming coupler weights are 0.56 g/mZ and 1.24 g/mZ, respectively (Reference film 1).
Following the procedure described for film 1, films 2, 3 and 4 according to this invention were prepared on substitution of 1-phenyl-5-mercaptotetrazole with 48 micromol, 96 micromol and 192 micromol per mole of silver, respectively, of 1-(2-trifluoromethylphenyl)-5-mercapto-tetrazole.
Samples of the films were stored for 24 hours to 21%, 50% and 80% relative humidity, respectively, then each sample was sealed in a package impervious to humidity and stored for three days at 33 D C .
Each of the film samples was exposed through an opti-cal wedge using an infrared sensitometer. After exposure, these samples were processed in a standard Kodak EP-2 pro-cessing color chemistxy with conditions similar to those stated in US Pat. No. 4,346,873.
After processing, status D densitometry was measured.
Table 4 reports the. variations of sensitivity versus the reference sample stored at 50% relative humidity (S) and the change in sensitivity among samples stored at 21% and 50% relative humidity (dSl) and among samples stored at 21% and 50% relative humidity (dS2). The values of sensi-tivity a~e expressed in log E units necessary to have an optical density of 1Ø
203't~35(~
Tabl~ 4 __ ______________________________________________________ Film S dSl dS2 _________________________________________________________ 1,00 (ref. ) +0,05 -0,49 2 -0 ,16 -0, 03 -0, 40 3 +0, 08 0, 00 -0, 30 4 +0,23 -0,02 -0,31 ______________________________ _______________.___________
Pat. No. 3,458,318, pyrimidine derivatives described in US
Pat. No. 3,615,632, azaindene compounds described in US
_ 3 - Z0~4850 Pat. No. 4,011,083, triaryl compounds described in US Pat.
No. 4,578,347, thiazolium and oxazolium salts described in US Pat. No. 4,596,767, combinations of supersensitizers described in US Pat. No. 4,603,104 and thiatriazoles described in US Pat. No. 4,780,404.
Photographic elements comprising silver halide emul-sion layers sensitized to infrared regions of the electro-magnetic spectrum, in particular color photographic ele-ments associated with photographic color image forming materials, are generally liable to undergo changes in sen-sitivity if stored under different conditions of humidity and temperature. Such change in photographic sensitivity is a critical problem in the use of infrared sensitized photographic materials. It is well known that commercial-ly available photographic materials having sensitivity in the infrared region are unstable in sensitivity and re-quire special caution for preservation thereof, such as storage in a refrigerator. Conventionally known stabiliz-ers such as 1-phenyl-5-mercaptotetrazole are not effective for improving stability of infrared sensitized photograph-ic materials. Therefore, a need exists to develop a tech-nique wich specifically improves the stability on storage of infrared sensitized emulsions.
Mercaptotetrazoles are generally disclosed in US Pat.
Nos. 3,Z66,897 (carboxysubstituted mercapto tetrazoles for use as antifoggants in silver halide emulsions) and 3,397,987 (heterocyclic nitrogen compounds containing a mercapto function for use as development fog inhibitors in silver halide emulsions comprising unfogged surface latent image grains and fogged internal image silver halide grains).
US Pat. No. 3,637,393 describes the use of mer-captotetrazoles in combination with certain hydroquinone compounds to reduce fog and increase speed in silver halide color photographic emulsions.
US Pat. No. 3,457,078 describes the use of mercapto substituted oxazine, oxazole, thiazole, thidiazole, - ~ - 20;~4850 imidazole, or tetrazole, the mercapto substituted compound further containing an electronegative substituent, as supersensitizers and antifoggants in combination with cer-tain cyanine dyes. 1-Phenyl-2-mercaptotetrazole is a suit-able substance disclosed in said patent.
Japanese Pat. Appln. No. J0 1013-539 describes the combined use of mercaptotriazole derivatives and mercaptotetrazole derivatives as supersensitizers in in-frared sensitive silver halide materials.
US Pat. No. 4,603,104 describes the combined use of arylmercaptotetrazoles and others supersensitizers tb in-crease the speed of spectrally sensitized silver halide photographic emulsions.
SUMMARY OF THE INVENTION
An infrared sensitive photographic element is dis-closed which comprises at least one silver halide emulsion layer spectrally sensitized to the infrared portion of the electromagnetic spectrum. In particular, the element com-prises at least three silver halide emulsion layers on a substrate, each associated with different photographic color image forming materials, such as color couplers ca-pable of forming dyes of different colors upon reaction with an o~idized color photographic developer, diffusing dyes, bleachable dyes, or o~idized leuco dyes. The three emulsion layers are sensitized to three different portions of the electromagnetic spectrum with at least two ~ayers sensitized to different regions of the infrared region of the electromagnetic spectrum. The element is characterized in that at least one infrared sensitized emulsion layer is associated with an 1-aryl-5-mercaptotetrazole compound substituted in the aryl group by at least one electron-attracting group.
The infrared sensitive photographic element has high sensitivity to infrared radiation and undergoes less change in sensitivity during storage.
;2034850 DETAILED DESCRIPTION OF THE INVENTION
An infrared sensitive photographic element is herein described which element comprises a support and one or more silver halide emulsion layers, at least one silver halide emulsion layer being spectrally sensitized to the infrared portion of the electromagnetic spectrum. In par-ticular, an infrared sensitive color photographic element is herein described which element is capable of providing a full color image or three color images with exposure of at least two silver halide emulsion layers to radiation outside the visible region of the electromagnetic spec-trum, which element comprises a substrate, and on one side of said substrate at least three silver halide emulsion layers, each of said silver halide emulsion layers being associated with means for forming a single color image of a different color dye, said three emulsion layers being sensitized to three different portions of the electromag-netic spectrum with at least two layers sensitized to dif-ferent regions of the infrared region of the electromag-netic spectrum. The element is characterized in that at least one infrared sensitized emulsion layer is associated with an 1-aryl-5-mercaptotetrazole compound substituted in the-aryl group by at least one electron-attracting group.
Preferably, the compounds of the present invention are represented by the structural formula (I) N N
N~ ~C-SH
Ar wherein Ar is an aryl group bearing at least one electron-attracting group. More preferably, the aryl group is a phenyl group and the electron-attracting groups are selected from the group consisting of nitro, cyano, - 6 - 2034~50 fluoroalkyl, halogen (preferably, chlorine or bromine), carbamoyl (preferably, a C1 to C4 straight or branched alkylaminocarbonyl or an unsubstituted or substituted phenylaminocarbonyl group), sulfamoyl (preferably, a Cl to C4 straight or branched alkylaminosulfonyl or an unsubstituted or substituted phenylaminosulfonyl group), acylamino (preferably, a C1 to C4 straight or branched alkylcarbonamido or an unsubstituted or substituted phen-ylcarbonamido group), sulfonamido (preferably, a C1 to C4 straight or branched alkylsulfonamido or an unsubstituted or substituted phenylsulfonamido group) and acyl (prefera-bly, a C1 to C~ straight or branched alkylcarbonyl or an unsubstituted or substituted phenylcarbonyl group).
Still more preferably, the compounds of the present invention are represented by the structural formula (I) wherein Ar is a phenyl group bearing one or more Cl to C~
straight or branched fluoroalkyl groups, wherein the alkyl group has at least one fluorine atom per carbon atom, preferably at least 1.5 fluorine atoms per carbon atom, more preferably all hydrogen atoms substituted with fluo-rine atoms.
When the term "group" is used in this invention to describe a chemical compound or substituent, the described chemi~al material includes the basic group and that group with conventional substitution. Where the term "moiety" is used to describe a chemical compound or substituent, only an unsubstituted chemical material is intended to be in-cluded. For example, "alkyl group" includes not only such alkyl moieties as methyl, ethyl, octyl, stearyl, etc., but also such moieties bearing substituent groups such as halogen, cyano, hydroxyl, nitro, amine, carboxylate, etc.
On the other hand, "alkyl moiety" includes only methyl, ethyl, octyl, stearyl, cyclohexyl, etc.
Specific examples of aryl groups substituted with one or more electron-attracting groups are, for example, a 4-nitrophenyl group, 2-nitro-4-N,N-dimethylsulfamoylphenyl group, 2-N,N-dimethylsulfamoyl-4-nitrophenyl group, , ~ 7 ~ 203~850 2-cyano-4-methylsulfonylphenyl group, 2,4-dinitrophenyl group, 2,4,6-tricyanophenyl group, 2-nitro-4-N,N-dimethyl-carbamoylphenyl group, 2,4-dimethanesulfonylphenyl group, 3,5-dinitrophenyl group, 2-chloro-4-nitro-5-methylphenyl group, 2-nitro-3,5-dimethyl-4-tetradecylsulfonylphenyl group, 2,4-dinitronaphthyl group, 2-ethylcarbamoyl-4-nitrophenyl group, 3,5-bistrifluoromethylphenyl group, 2,3,4,5,6-pentafluorophenyl group, 3-acetamidophenyl group, 2-acetyl-4-nitrophenyl group, 2,4-diacetylphenyl group, 2-nitro-4-trifluoromethyl phenyl group, 4-ethoxy-carbonyl phenyl group.
The compounds of the present invention represented by the general formula (I) may be added in any effective sta-bilizing amount to the photographic emulsion. The concen-tration of said compounds can vary significantly in photo-graphic emulsions. A generally useful range would be from 0.008 to 0.28 g per mol of silver. A more preferred range would be from 0.015 to 0.150 g per mol of silver. The com-pounds of the present invention can be directly dispersed in the photographic emulsion, or may be dissolved in a suitable solvent (e.g., water, methyl alcohol, ethyl alco-hol, propanol, methyl cellosolve, acetone, etc.) or in a mixture of these solvents and added as a solution to the emulsion. In addition, said compounds can be added to the emulsion as a solution or as a colloid dispersion accord-ing to the processes for adding sensitizing dyes, as known to those skilled in the art.
Any spectral sensitizing dye known to sensitize sil-ver halide emulsions to infrared portion of the electro-magnetic spectrum may be used in the practice of the present invention with the stabilizer compounds of the present invention. The infrared portion of the electromag-netic spectrum is given various ranges, but is generally considered to be between 750 and 1500 nm which overlaps a small portion of the visible regions of the electromagnet-ic spectrum (e.g., about 750-780 nm). Useful dyes for this - 8 - Z 0 3 4 85 ~
purpose tend to be merocyanines, cyanines and especially tricarbocyanines. Such dye sensitizers for the infrared are described for example in US Pat. Nos. 3,457,078, 3,619,154, 3,682,630, 3,690,891, 3,695,888, 4,030,932 and 4,367,800. The preferred classes of dyes are the tricarbocyanines such as 3,3'-dialkylthiatricarbocyanines, thiatricarbocyanines (especially with rigidized chains), selenotricarbocyanines, and enamine tricarbocyanines.
Preferred classes of dyes according to the present invention are represented by the following general formula (II) or (III):
R2 ~3 / C (II) Ro-N-(CH=CH)n-C=CH-C=CH-C=CH-CH=CH-C(=CH-CH)~=N+Rl Z1 1 14 _ Z2 (III) Ro~N~( CH=CH)n-C=CH-C=CH-C=CH-CH=CH-C(=CH-CH)~=N~R
X
wherein:
Ro and R1 can be a substituted alkyl group or a nonsubstituted alkylgroup having from 1 to 8 carbon atoms such as , for example, methyl, ethyl, propyl, butyl, amyl, benzyl, octyl, carboxymethyl, carboxyethyl, sulfopropyl, carboxypropyl, carboxybutyl, sulfoethyl,- sulfoisopropyl and sulfobutyl groups;
X-is any acid anion such as, for example, chloride, bromide, iodide, tri-iodide, perchlorate, sulfamate, thio-cyanate, p-toluenesulfonate and benzenesulfonate;
Z1 and Z2 are independently the non-metallic atoms necessary to complete an aromatic heterocyclic nucleus chosen within those of the thiazole series, benzothiazole series, (i,2-d)-naphthothiazole series, (2,1-d)-naphtho-thiazole series, oxazole series, benzoxazole series, - 9- Z0~4850 selenazole series, benzoselenazole series, (1,2-d)-naphthoselenazole series, ~2,1-d)-naphthoselenazole series, thiazoline series, 4-quinoline series, 2-pyridine series, 4-pyridine series, 3,3'-dialkyl-indolenine series (wherein alkyl has a meaning known to those skilled in the art including alkyl groups having 1 to 12 carbon atoms), imidazole series and benzimidazole series.
More particularly and preferably, the present inven-tion refers to dyes of the type above indicated in which both heterocyclic nuclei are of the benzothiazole series.
R2 and R3 each represent a hydrogen atom, or an alkyl goup having 1 to 5 carbon atoms such as a methyl group or an ethyl group; R~ represents a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 5 car-bon atoms, an unsubstituted or substituted aryl group, an acyloxy group shown by -C-O-Rs wherein Rs represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a su~stituted phenyl group.
The infrared sensitizing dyes of the present inven-tion are incorporated in the silver halide photographic emulsion in a content of 5xlO-7mol to 5xlO~3mol, prefer-ably lxlO- 6 mol to lxlO-3mol, more preferably 2~10- 6 mol to 5xlO-~mol, per mol of silver.
The infrared sensitizing dyes to be used in the present invention can be directly dispersed in the emul-sion. Alternatively, they may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixture thereof to add them to the emulsion as a solution. Pro-cesses for adding the infrared sensitizing dyes to the photographic emulsion are described, for example, in US
Pat. Nos. 3,469,987, 3,676,147, 3,822,135, 4,199,360, and in US Pat. Nos. 2,912,343, 3,342,605, 2,996,287 and 3,429,83S; The aforesaid infrared sensiti~ing dyes may be - 10- ~03485(~
uniformly dispersed in the silver halide emulsion before coating on a suitable support~ Of course, this dispersing procedure may be conducted in any step of preparing the silver halide emulsion.
The ratio (by wei~ht) of the amount of the infrared sensitizing dye to that of the compound represented by the general formula (I) is advantageously 1/1 to 1/30, partic-ularly advantageously 1/2 to lt50.
Infrared sensitive silver halide photographic ele-ments for use in the present invention are preferably those described in US Pat. No. 4,619,892, which is incor-porated herein by reference. More preferably, the infrared sensitive silver halide color photographic elements for use in the present invention are those having all of the silver halide emulsion layers sensitized to different in-frared regions of the electromagnetic spectrum. The order of these layers respect to the support, the difference in emulsion sensitivity among the layers and the sensitivity, contrast and D-max of each layer are preferably those de-scribed in said US Pat. No. 4,619,892.
Any of the various types of photographic silver halide emulsions may be used in the practice of the present invention. Silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and mixture thereof may be used, for example, dispersed in a hydrophilic colloid or carrier.
Any configuration of grains, cubic, orthorombic, hexago-nal, epitaxial, or tabular (high aspect ratio) grains may be used. The colloid may be partially hardened or fully hardened by any of the variously known photographic hard-eners. Such hardeners are free aldehydes, aldehyde releas-ing comounds, triazines and diazines, aziridines, vinylsulfones, carbodiimides, and the like may be used, as described, for example, in US Pat. Nos. 3,232,764, 2,870,013, 3,819,608, 3,325,287, 3,992,366, 3,271,175 and 3,490,911;
The silver halide photographic elements can be used ;~0348S0 to form dye images therein through the selective formation of dyes. The photographic elements described above for forming silver images can be used to form dye images by employing developers containing dye image formers, such as color couplers, as described, for example, in US Pat. Nos.
3,111,864, 3,002,836, 2,271,238, 2,Z36,598, 2,950,970, 2,592,243, 2,3~3,703, 2,376,380, 2,369,489, 2,899,306, 3,152,896, 2,115,394, 2,252,718, 2,108,602, and 3,547,650.
In this form the developer contains a color developing agent (e.g., a primary aromatic amine which in its oxi-dized form is capable of reacting with the coupler to form the image dye). Also, instant self-developing diffusion transfer film can be used as well as photothermographic color film or paper using silver halide in catalytic pro~-imity to reducable silver sources and leuco dyes.
The dye-forming couplers can be incorporated in the photographic elements, as illustrated by Schneider et al., Die Chemie, Vol. 57, 1944, p.113, and in US Pat. Nos.
2,304,940, Z,269,158, 2,322,027, 2,376,679, 2,801,171, 2,748,141, 2,772,163, 2,835,579, 2,533,514, 2,353,754, 3,409,435 and Chen, Research Disclosure, Vol. 159, July 1977, Item 15930. The dye-forming couplers can be incorpo-rated in different amounts to achieve differing photo-graphic effects. For example, GB Pat. No. 923,045 and US
Pat. No. 3,843,369 teach limiting the concentration of coupler in relation to the silver coverage to less than normally employed amounts in faster and intermediate speed emulsion layers.
The dye-forming couplers are commonly chosen to form subtractive primary (i.e., yellow, magenta and cyan) image dyes and are nondiffusible, colorless couplers, such as two and four equivalent couplers of the open chain keto-methylene, pyrazolone, pyrazolotriazole, pyrazolobenz-imidazole, phenol and naphthol type hydrophobically bal-lasted for incorporation in high-boiling organic (coupler) solvents: Such couplers are illustrated in US Pat. Nos.
2,423,730, 2,772,162, 2,895,826, 2,710,803, 2,407,207, 3,737,316, 2,367,531, 2,772,161, 2,600,788, 3,006,759, 3,214,437, 3,253,924, 2,875,057, 2,908,573, 3,043,892, 2,474,293, 2,407,210, 3,06~,653, 3,265,506, 3,384,657, 2,343,703, 3,127,269, 2,865,748, 2,933,391, 2,865,751, 3,725,067, 3,758,308, 3,779,763, 3,785,829, 3,762,921, 3,983,608, 3,311,467, 3,408,194, 3,458,315, 3,4~7,928, 3,476,563, 3,419,390, 3,419,391, 3,519,429, 3,222,176, 3,227,550, in GB Pat. Nos. 969,921, 1,241,069, 1,011,940, 975,928, 1,111,554, 1,248,g24, and in CA Pat. No. 726,651.
Dye-forming couplers of differing reaction rates in single or separate layers can be employed to achieve desired ef-fects for specific photographic applications.
The dye-forming couplers upon coupling can release photographically useful fragments, such as development inhibitors or accelerators, bleach accelerators, develop-ing agents, silver halide solvents, toners, hardeners, fogging agents, antifoggants, competing couplers, chemical or spectral sensitizers and desensitizers. Development inhibitor-releasing (DIR) couplers are illustrated in US
Pat. Nos. 3,148,062, 3,227,554, 3,733,201, 3,617,291, 3,703,375, 3,61~,506, 3,265,506, 3,620,745, 3,632,345, 3,869,Z91, 3,642,485, 3,770,436, 3,808,945, and in GB Pat.
Nos. 1,201,110 and 1,236,767. Dye-forming couplers and nondye-forming compounds which upon coupling release a variety of photographically useful groups are described in US Pat. No. 4,248,962. DIR compounds which do not form dye upon reaction with oxidized color developing agents can be employed, as illustrated in US Pat. Nos. 3,928,041, 3,958,993, 3,961,959, 4,049,455, 4,052,213 and in German OLS Nos. 2,529,350, 2,448,063 and 2,610,546. DIR compounds with oxidatively cleave can be employed, as illustrated in US Pat. Nos. 3,379,529, 3,043,690, 3,364,022, 3,297,445 and 3,287,129. Silver halide emulsions which are relative-ly light insensitive, such as Lipmann emulsions, having been used as interlayers or overcoat layers to prevent or control t~e migration of development inhibitor fragments - 13 - 203~ 850 as described in US Pat. No. 3,892,572.
The photographic elements can incorporate colored dye-forming couplers, such as those employed to form inte-gral masks for negative color images, as illustrated in US
Pat. Nos. 2,449,966, 2,521,908, 3,034,892, 3,476,563, 3,519,429, 2,543,691, 3,028,238, 3,061,432, and/or compet-ing couplers, as illustrated in US Pat. Nos. 3,876,428, 3,580,722, 2,998,314, 2,808,329, 2,742,832 and 2,689,793.
As previously noted, the color provided in the image produced by exposure of each of the dif~erently sensitized silver halide emulsion layers does not have to be produced by color coupler reaction with oxidized color developers.
A number of other color image forming mechanisms well known in the art can also be used. Amongst the commercial-ly available color image forming mechanisms are the diffu-sion transfer of dyes, dye-bleaching, and leuco dye oxi-dation. Each of these procedures is used in commercial products, is well understood by the ordinary skilled pho-tographic artisan, and is used with silver halide emul-sions. Multicolor elements using these different technolo-gies are also commercially available. Converting the ex-isting commercially available systems to the practice of the present invention could be done by routine redesign of the sensitometric parameters of the system and/or the ad-dition of intermediate filter layers as described in US
Pat. No. 4,519,892. For example, in a conventional instant color dye-diffusion transfer element, the sensitivity of the various layers and/or the arrangement of filter layers between the silver halide emulsion layers would be direct-ed by the teachings of the above US patent, the element otherwise remaining the same. This would be true with ei-ther negative-acting or positive-acting silver halide emulsions in the element. The only major, and fairly ap-parent, consideration that must be given to such construc-tion is to insure that the placement of any filter layers does not prevent transfer of the diffusion dye to a recep-tor layer within the element. Using a filter which is not , .
a barrier layer between the receptor layer and the dye-containing layer is the simplest way to address that consideration. Such a layer should not prevent migration of the diffusion dye across the filter layer.
These types of imaging systems are well knawn in the art. Detailed discussions of various dye transfer, diffu-sion processes may be found for example in "A fundamental-ly New Imaging Technology for Instant Photography", W.T.
Harison, Jr., Photographic Science and Engineering, Vol.
20, No. 4, July~August 1976, and Neblette's Handbook of photography and Reprography, Materials, Processes and-Sys-tems, 7th Edition, John. M. Stunge, van Nostrand Reinhold Company, N.Y., 1977, pp. 324-330 and 126. Detailed dis-cussion of dye-bleach color imaging systems are found for example in The Reproduction of Colour, 3rd Ed., R.W.G.
Hunt, Fountain Press, London, England, 1975, pp.325-330;
and The Theory of the Photographic Process, 4th Ed., Mees and ~ames, Macmillan Publishing Co., Inc., N.Y., 1977, pp.
363-366. Pages 366-372 of Mees and James, supra, also dis-cuss dye-transfer processes in great detail. Leuco dye oxidation in silver halide systems are disclosed in such literature as US Pat. Nos. 4,460,681, 4,374,821, and 4,021,240. Diffusion photothermographic color image form-ing systems such as those disclosed in GB Pat. Appln. No.
3,100,458 are also useful in the practice of the present invention.
The photographic elements can include image dye sta-bilizers. Such image dye stabilizers are illustrated in US
Pat. Nos. 3,432,300, 3,698,909, 3,574,627, 3,573,050, 3,764,337, and 4,042,394 and in GB Pat. No. 1,326,889.
Filter dyes can be included in the photographic ele-ments. Said dyes must be selected on the basis of their radiation filtering characteristics to insure that they filter the appropriate wavelengths. Filter dyes and their methods of incorporation into the photographic elements are well-documented in the literature such as US Pat. Nos.
4,440,852, 3,671,648, 3,423,207, and 2,895,955, GB Pat.
.
- 15 - 203~85~
No. 485,624, and Research Disclosure, Vol. 176, December 1978, Item 17643. Filter dyes can be used in the practice of the present invention to provide room-light handleability to the elemen~s. Dyes which will not allow tran~mission of radiation having wavelengths shorter than the shortest wavelength to which one of the emulsion lay-ers has been sensitized can be used in a layer above one or more (preferably all) of the emulsion layers. The cut-off filter dye preferably does not transmit light more than approximately 50 nm less than the shortest wavelength to which any of the emulsion layers have been sensitized.
Filter dyes should also be provided with non-fugitive (i.e., non-migratory) characteristics and should be decolorizable (by bleaching in developer or heat, for ex-ample) or leachable ~e.g., removed by solvent action of any baths).
Other conventional photographic addenda such as coat-ing aids, antistatic agents, acutance dyes, antihalation dyes and layers, antifoggants, latent image stabilizers, antikinking agents, high intensity reciprocity failure reducers, and the like may also be present.
The following examples illustrate a general synthetic procedure which may be used in the preparation of 1-aryl-5-mercaptophenyltetrazole derivatives and non-limiting examples of preferred embodiments of the present inven-tion.
Preparation of 1-(3,5-bistrifluoromethylphenyl)-5-mer-captotetrazole a) 0.052 Mol of thiophosgene were mixed with 60 ml of water and were stirred for 15 minutes. 0.040 Mol of 3,5-bistrifluoromethylaniline were dropped with 30 ml chloroform, and the mixture was stirred for 2 hours at 15C. The organic solution was washed with HCl 2M, dried and the solvent was removed under vacuum to obtain 3,5-bistrifluoromethylphenylisothiocyanate as a yel~ow-red oil, that was used as crude product.
b) 0.040 Mol of the isothiocyanate above and 0.060 mol sodium azide were added to 100 ml of water and re-fluxed for 7 hours. The mi~ture was cooled, filtered, washed twice with ethyl ether to separate the unreacted isothiocyanate, then the solution pH was adjusted to 2.5.
The solid ma~erial which formed was filtered and recrystallized from carbon tetrachloride. Analytical data (IR, NMR, elemental analysis) confirmed the chemical structure.
A photographic emulsion was prepared by precipitation of AgCl and c~nversion to AgBr to provide an emulsion with 85% bromide and 15% chloride with an average grain size of 0.4 micrometers. The emulsion was chemically digested with sodium thiosulfate, added with a dispersion of the magenta dye forming coupler A in a water-insoluble high boiling organic solvent to have a coupler amount of 240.95 g per mol of sil~er, with 1-phenyl-5-mercaptotetrazole as super-sensitizer and stabilizer in a quantity of 127 micromol per mol of silver and sensitized to the 820 nm region of the spectrum with dye B in the quantity of 93xlO- 6 mol per mol of silver. This emulsion, added with conventional surfactants and hardeners, was coated onto a paper support so that the coating silver and the magenta dye forming coupler weights are 0.56 g/m~ and 1.24 g/mZ, respectively (Reference film 1).
Following the procedure described for film 1, films 2 and 3 according to this invention were prepared on substi-tution of 1-phenyl-5-mercaptotetrazole with 36 micromol and 142 micromol per mole of silver, respectively, of 1-(3,5-bistrifluoromethylphenyl)-5-mercaptotetrazole.
Samples of the films were stored for 24 hours to 21%, 50~ and 80%, respectively, relative humidity, then each .
sample was sealed in a sealed bag and stored for three days at 33 C. Each of the film samples was e~posed through an optical wedge using an infrared sensitometer. After e~posure, these samples were processed in a standard Kodak ~P-2 processing color chemistry with conditions similar to those stated in US Pat. No. 4,3~6,873.
After processing, status D densitometry was measured.
Table 1 reports the variations of sensitivity versus the-reference sample stored at 50~ relative humidity (S) and the change in sensitivity amon~ samples stored at 21% and 50% relative humidity (dS$) and among samples stored at 21~ and 50% relative humidity (dSz). The values of sensi-tivity are e~pressed in log E units necessary to have an optical density of 1Ø
Table 1 _________________________________________________________ Film S dS1 dSz _________________________________________________________ 1 1,00 (ref.) +0,10 -0,08 2 -0,01 +0,02 -0,03 3 +0,28 +0,02 -0,01 _________________________________________________________ Coupler A:
O~ O= ~ -CH=CH-C16H33 Cl~ ~ ,Cl Cl - 18 - 203~50 Dye B:
H3C ~ ~CH3 1~ + C-CH=C C-CH=CH-CH=C~) H3 C ~ \ N~ N
A photographic emulsion was prepared by precipitation of AgCl and conversion to AgBr to provide an emulsion with 85% bromide and 15~ chloride with an average grain size of 0.9 micrometers. The emulsion was chemically digested with sodium thiosulfate, added with a dispersion of the cyan dye forming coupler C in a water-insoluble high boiling organic solvent to have a coupler amount of 164.68 g per mol of silver, with 1-phenyl-5-mercaptotetrazole as supersensitizer and stabilizer in a quantity of 5~
micromol per mol of silver and sensitized to the 895 nm region of the spectrum with dye D in the quantity of 45.5xlO- 6 mol per mol of silver. This emulsion, added with conventional surfactants and hardeners, was coated onto a paper support so that the coating silver and the cyan dye forming coupler weights are 0.42 g/m2 and 0.64 g/mZ, re-spectively (Reference film 1).
Following the procedure described for film 1, films 2 and 3 according to this invention were prepared on substi-tution of 1-phenyl-5-mercaptotetrazole with 439 micromol and 8~9 micromol per mole of silver, respectively, of 1-(3,5-bistrifluoromethylphenyl)-5-mercaptotetrazole.
Samples of the films were stored for 24 hours to 21~, 50~ and 80% relative humidity, respectively, then each sample was sealed in a sealed bag and stored for three days at 33~C.
Eacn of the film samples was exposed through an opti-cal wedge using an infrared sensitometer. After exposure, - 19 - 2034~350 these samples were processed in a standard Xodak EP-2 pro-cessing color chemistry with conditions similar to those stated in US Pat. No. 4,346,873.
After processing, status D densitometry was measured.
Table 2 reports the variations of sensitivity versus the reference sample stored at 50% relative humidity (S) and the change in sensitivity among samples stored at 21% and 50% relative humidity- (dSl) and among samples stored at 21% and 50% relative humidity (dS2). The values of sensi-tivity are e~pressed in log E units necessary to have an optical density of 1Ø
Table 2 _________________________________________________________ Film S dS1 dS2 _________________________________________________________ 1 1,00 (ref.) +0,10 -0,38 2 -0,17 0,00 -0,04 3 -0,0~ 0,00 0,00 _________________________________________________________ Coupler C:
OH O H1lCs Cl ~ NH-C-CH-O ~ CsH
H3C ~ C2Hs Cl -Dye D:
~Cl Cl .' ~ ~ ' HsC2-N ~ CH=CH-CH=CH-CH~ ~ N-C2Hs I-E~AMPLE 4 A photographic emulsion was prepared by precipitation of AgCl and conversion to AgBr to provide an emulsion with 85~ bromide and 15% chloride with an average grain size of 0.9 micrometers. The emulsion was chemically digested with sodium thiosulfate, added with a dispersion of the yellow dye forming coupler E in a water-insoluble high boiling organic solvent to have a coupler amount of 157.95 g per mol of silver, with 1-phenyl-5-mercaptotetrazole as super-sensitizer and stabilizer in a quantity of 10 micromol per mol of silver and sensitized to the 760 nm region of the spectrum with dye F in the quantity of 258.4xlO- 6 mol per mol of silver. This emulsion, added with conventional surfactants and hardeners, was coated onto a paper support so that the coating silver and the yellow dye forming cou-pler weights are 0.56 g/m2 and 0.84 g/m2, respectively (Reference film 1).
Following the procedure described for film 1, films 2 and 3 according to this invention were prepared on substi-tution of 1-phenyl-5-mercaptotetrazole with 289 micromol and 578 micromol per mole of silver, respectively, of 1-(3,5-bistrifluoromethylphenyl)-5-mercaptotetrazole.
Samples of the films were stored for 24 hours to 21%, 50~ and 80% relative humidity, respectively, then each sample was sealed in a sealed bag and stored for three days at 33 C.
Each of the film samples was exposed through an opti-cal wedge using an infrared sensitometer. After exposure, these samples were processed in a standard Kodak EP-2 pro-cessing color chemistry with conditions similar to those stated in US Pat. No. 4,346,873.
After processing, status D densitometry was measured.
Table 3 reports the variations of sensitivity versus the reference sample stored at 50~ relative humidity (S) and the change in sensitivity among samples stored at 21~ and 50~ relative humidity (dS1) and among samples stored at ' .
, - 2.~ -21~ and 50% relative humidity (dS2). The values of sensi-tivity are expressed in log E units necessarY to have an optical density of 1Ø
Table 3 _________________________________________________________ Film S dSl dS2 ________________________________________________._________ 1 1,00 (ref.) +0,04 -0,30 2 -0,03 ~0,04 -0,19 3 +0,01 +0,02 -0,13 Coupler E:
CH3 Cl CH3-C-CO - CH-CO-NH- ~ Hl1Cs HC N NH-CO-(CH2)3-O ~ CsH
Il 11 N - C
l \
N O
Dye F:
f2Hs ~-CH=CH-CH=CH-CH ~ I-A phQtographic emulsion was prepared by precipitation of AgCl and conversion to AgBr to provide an e~ulsion with 203~185(~
85~ bromide and 15% chloride with an average grain size of 0.4 micrometers. The emulsion was chemically digested with sodium thiosulfate, added with a dispersion of the magenta dye forming coupler A of Example 1 in a water-insoluble high boiling organic solvent to have a coupler amount of 240.95 g per mol of silver, with 1-phenyl-5-mercaPto-tetrazole as supersensitizer and stabilizer in a quantity of 127 micromol per mol of silver and sensitized to the 820 nm region of the spectrum with dye B of Example 1 in the quantity of 93xlO- 6 mol per mol of silver. This emul-sion, added with conventional surfactants and hardeners,was coated onto a polyester support so that the coating silver and the magenta dye forming coupler weights are 0.56 g/mZ and 1.24 g/mZ, respectively (Reference film 1).
Following the procedure described for film 1, films 2, 3 and 4 according to this invention were prepared on substitution of 1-phenyl-5-mercaptotetrazole with 48 micromol, 96 micromol and 192 micromol per mole of silver, respectively, of 1-(2-trifluoromethylphenyl)-5-mercapto-tetrazole.
Samples of the films were stored for 24 hours to 21%, 50% and 80% relative humidity, respectively, then each sample was sealed in a package impervious to humidity and stored for three days at 33 D C .
Each of the film samples was exposed through an opti-cal wedge using an infrared sensitometer. After exposure, these samples were processed in a standard Kodak EP-2 pro-cessing color chemistxy with conditions similar to those stated in US Pat. No. 4,346,873.
After processing, status D densitometry was measured.
Table 4 reports the. variations of sensitivity versus the reference sample stored at 50% relative humidity (S) and the change in sensitivity among samples stored at 21% and 50% relative humidity (dSl) and among samples stored at 21% and 50% relative humidity (dS2). The values of sensi-tivity a~e expressed in log E units necessary to have an optical density of 1Ø
203't~35(~
Tabl~ 4 __ ______________________________________________________ Film S dSl dS2 _________________________________________________________ 1,00 (ref. ) +0,05 -0,49 2 -0 ,16 -0, 03 -0, 40 3 +0, 08 0, 00 -0, 30 4 +0,23 -0,02 -0,31 ______________________________ _______________.___________
Claims (7)
1. A silver halide photographic element comprising a support and at least one silver halide emulsion layer spectrally sensitized to the infrared portion of the elec-tromagnetic spectrum, characterized in that said infrared sensitized emulsion layer is associated with a 1-aryl-5-mercaptotetrazole compound substituted in the aryl group by at least one electron-attracting group.
2. The silver halide photographic element of claim comprising a support, and on one side of said support at least three silver halide emulsion layers, each of said silver halide emulsion being associated with a different color photographic coupler, each emulsion layer being sen-sitized to a different region of the electromagnetic spec-trum and at least two emulsion layers being sensitized to radiation within the infrared region of the electromag-netic spectrum, characterized in that at least one of said infrared sensitized emulsion layer is associated with the 1-aryl-5-mercaptotetrazole compound substituted in the aryl group by at least one electron-attracting group.
3. The photographic element of claim 1 wherein said compound is represented by the structural formula:
wherein Ar is an aryl group bearing an electron- attract-ing group.
wherein Ar is an aryl group bearing an electron- attract-ing group.
4. The photographic element of claim 1 wherein the aryl group is a phenyl group.
5. The photographic element of claim 1 wherein the electron-attracting group is selected from the group con-sisting of nitro, cyano, fluoroalkyl, halogen, carbamoyl, sulfamoyl, acylamino, sulfonamido and acyl.
6. The photographic element of claim 1 wherein the arylmercaptotetrazole derivative is present in an amount from about 0.008 g to about 0.280 g per mole of silver halide.
7. The photographic element of claim 1 wherein the silver halide emulsion associated with the arylmercaptote-trazole compound substituted in the aryl group by at least one electron-attracting group is sensitized by a dye se-lected form the class consisting of thia-, benzothia-, seleno-, benzoseleno-, imida-, benzoimida-, oxa-, benz-oxa-, and enaminetricarbocyanines.
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IT19235-A/90 | 1990-02-01 | ||
IT01923590A IT1237964B (en) | 1990-02-01 | 1990-02-01 | INFRARED SENSITIVE SILVER HALIDE PHOTOGRAPHIC ELEMENTS |
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CA002034850A Abandoned CA2034850A1 (en) | 1990-02-01 | 1991-01-24 | Infrared sensitive silver halide color photographic elements |
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US (1) | US5543278A (en) |
EP (1) | EP0440947B1 (en) |
JP (1) | JPH04213450A (en) |
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AU (1) | AU634626B2 (en) |
CA (1) | CA2034850A1 (en) |
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IT (1) | IT1237964B (en) |
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IT1271047B (en) * | 1994-10-26 | 1997-05-26 | Minnesota Mining & Mfg | SILVER HALIDE PHOTOGRAPHIC ELEMENT AND METHOD TO STABILIZE AN EMULSION TO LIGHT SENSITIVE SILVER HALIDE |
DE19810932A1 (en) | 1998-03-13 | 1999-09-16 | Bayer Ag | Electrochromic arrangement based on poly (3,4-ethylenedioxy-thiophene) derivatives |
DE10149568A1 (en) * | 2001-10-08 | 2003-04-24 | Consequence Gmbh | Detection of amines, especially aminoacids formed in sequencing of peptides by Edman degradation, by forming reaction product with halo-substituted phenylisothiocyanate |
JP2003123939A (en) * | 2001-10-12 | 2003-04-25 | Sharp Corp | Ion generator and air conditioner |
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DE1447577B1 (en) * | 1964-03-11 | 1970-05-14 | Agfa Ag | Stabilized supersensitization of halogen silver emulsions |
JPS4913566B1 (en) * | 1970-09-04 | 1974-04-01 | ||
US3708303A (en) * | 1971-01-12 | 1973-01-02 | Eastman Kodak Co | Photographic elements and processes lithographic silver halide element containing a 1-(amidophenyl)-5-mercaptotetrazole sensitizing agent and development process of using same |
US4011083A (en) * | 1974-12-10 | 1977-03-08 | Eastman Kodak Company | Surface sensitive silver halide emulsion containing a silver complexing azaindene to reduce desensitization of optical sensitizing dye incorporated therein |
US4910179A (en) * | 1981-11-05 | 1990-03-20 | Union Oil Company Of California | ID catalyzed reactions and compositions for use therein |
US4619892A (en) * | 1985-03-08 | 1986-10-28 | Minnesota Mining And Manufacturing Company | Color photographic element containing three silver halide layers sensitive to infrared |
IT1185540B (en) * | 1985-03-18 | 1987-11-12 | Minnesota Mining & Mfg | SILVER HALIDE PHOTOGRAPHIC MATERIAL FOR TANNING DEVELOPMENT PROCEDURE TO PRODUCE A RELIEF IMAGE |
US4603104A (en) * | 1985-05-31 | 1986-07-29 | Minnesota Mining And Manufacturing Company | Supersensitization of silver halide emulsions |
JPH0652382B2 (en) * | 1986-10-20 | 1994-07-06 | 富士写真フイルム株式会社 | Silver halide photographic light-sensitive material and image forming method using the same |
US4910129A (en) * | 1987-04-17 | 1990-03-20 | Mitsubishi Paper Mills, Ltd. | Silver halide photographic light sensitive material |
JPS6413539A (en) * | 1987-07-07 | 1989-01-18 | Mitsubishi Paper Mills Ltd | Silver halide photographic sensitive material |
DE3719880A1 (en) * | 1987-06-13 | 1989-01-05 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC HEAT DEVELOPMENT PROCESS |
JPH0814682B2 (en) * | 1988-01-18 | 1996-02-14 | 富士写真フイルム株式会社 | Silver halide photosensitive material |
JPH02132432A (en) * | 1988-07-28 | 1990-05-21 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material and image forming method using same |
JPH0269736A (en) * | 1988-09-05 | 1990-03-08 | Konica Corp | Silver halide photographic sensitive material and processing method |
JPH0778612B2 (en) * | 1988-11-28 | 1995-08-23 | 富士写真フイルム株式会社 | Silver halide photographic light-sensitive material |
JP2578188B2 (en) * | 1988-12-22 | 1997-02-05 | 富士写真フイルム株式会社 | Silver halide photographic material |
JP2670876B2 (en) * | 1989-02-14 | 1997-10-29 | 富士写真フイルム株式会社 | Color image forming method |
US5061618A (en) * | 1989-09-26 | 1991-10-29 | Eastman Kodak Company | Infrared-sensitive photographic element |
US5108882A (en) * | 1989-09-26 | 1992-04-28 | Eastman Kodak Company | Infrared-sensitive photographic element containing at least two photosensitive layers |
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- 1990-02-01 IT IT01923590A patent/IT1237964B/en active IP Right Grant
- 1990-12-17 EP EP90124428A patent/EP0440947B1/en not_active Expired - Lifetime
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1991
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- 1991-01-31 JP JP3011178A patent/JPH04213450A/en active Pending
- 1991-01-31 AU AU70144/91A patent/AU634626B2/en not_active Ceased
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DE69030808T2 (en) | 1997-09-25 |
AU7014491A (en) | 1991-08-08 |
EP0440947A2 (en) | 1991-08-14 |
IT9019235A1 (en) | 1991-08-02 |
IT9019235A0 (en) | 1990-02-01 |
DE69030808D1 (en) | 1997-07-03 |
JPH04213450A (en) | 1992-08-04 |
US5543278A (en) | 1996-08-06 |
AU634626B2 (en) | 1993-02-25 |
EP0440947B1 (en) | 1997-05-28 |
IT1237964B (en) | 1993-06-19 |
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