EP0644458B1 - Infrared sensitive silver halide phototographic elements - Google Patents
Infrared sensitive silver halide phototographic elements Download PDFInfo
- Publication number
- EP0644458B1 EP0644458B1 EP19930115143 EP93115143A EP0644458B1 EP 0644458 B1 EP0644458 B1 EP 0644458B1 EP 19930115143 EP19930115143 EP 19930115143 EP 93115143 A EP93115143 A EP 93115143A EP 0644458 B1 EP0644458 B1 EP 0644458B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- group
- sensitized
- infrared
- 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.)
- Expired - Lifetime
Links
- -1 silver halide Chemical class 0.000 title claims description 74
- 229910052709 silver Inorganic materials 0.000 title claims description 55
- 239000004332 silver Substances 0.000 title claims description 54
- 239000000839 emulsion Substances 0.000 claims description 58
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 238000001228 spectrum Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 230000005855 radiation Effects 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 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
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 150000002081 enamines Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 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 description 53
- 239000010410 layer Substances 0.000 description 46
- 238000000034 method Methods 0.000 description 16
- 230000001235 sensitizing effect Effects 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000003112 inhibitor Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 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
- 239000011248 coating agent Substances 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
- 238000005516 engineering process Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003918 triazines Chemical class 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
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical compound SC1=NN=NN1 JAAIPIWKKXCNOC-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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical class C1=COC=N1 ZCQWOFVYLHDMMC-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
- 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
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 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
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004891 diazines Chemical class 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical class C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 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
- 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
- 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
- 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 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
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 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
- 238000002360 preparation method Methods 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 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
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 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
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 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
- 238000003325 tomography Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 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
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
Definitions
- This invention relates to silver halide photographic elements sensitive to infrared radiation.
- the present invention relates to color photographic elements 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 one infrared sensitized emulsion layer is associated with a mercaptotriazole antifogging agent.
- silver halide photographic elements can be spectrally sensitized to infrared radiation. See Mees and James, The Theory of Photographic Processes , 3rd edition, The MacMillan Company, 1966, pages 198 and 199. Silver halides are intrinsically sensitive only to light in the blue region of the spectrum. Therefore, when silver halides are to be exposed to other wavelengths of radiation, such as green light, red light or infrared radiation, a spectral sensitizing dye is required to render silver halide sensitive to such radiation. As known in the art, silver halides having adsorbed on the grains spectral sensitizing dyes can be made sensitive to radiation of a wavelength other than the intrinsic blue sensitivity.
- This false address elements comprise at least three silver halide emulsions layers on a substrate, each associated with different photographic color image forming materials and sensitized to three different portions of the spectrum with at least two layers sensitized to different regions of the infrared region of the spectrum.
- the object of the present invention is to obtain an infrared light-sensitive material that inhibits fog formation without diminishing speed upon development.
- An infrared sensitive photographic element which comprises at least one silver halide emulsion layer spectrally sensitized to the infrared portion of the electromagnetic spectrum.
- the element comprises at least three silver halide emulsion layers on a substrate, each associated with different photographic color image forming materials, such as color couplers 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 different portions of the electromagnetic spectrum with at least two layers 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 a 3-mercapto-1,2,4-triazole antifogging agent represented by the formula (I): wherein R 1 and R 2 each independently represents hydrogen or alkyl group, the sum of carbon atoms of R 1 and R 2 is 1 or 2, and at least one of R 1 and R 2 is a perfluoroalkyl group.
- a 3-mercapto-1,2,4-triazole antifogging agent represented by the formula (I): wherein R 1 and R 2 each independently represents hydrogen or alkyl group, the sum of carbon atoms of R 1 and R 2 is 1 or 2, and at least one of R 1 and R 2 is a perfluoroalkyl group.
- the infrared sensitive photographic element has high sensitivity to infrared radiation and reduces the fog formation.
- An infrared sensitive photographic element 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.
- an infrared sensitive color photographic element 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 spectrum, 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 color dye different from the color dyes of the other layers, said three emulsion layers being 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.
- the element is characterized in that at least one infrared sensitized emulsion layer is associated with a 3-mercapto-1,2,4-triazole antifogging agent of formula (I).
- alkyl groups for R 1 and R 2 are methyl and ethyl, which may themselves be substituted with known groups such as hydroxy and halogen (e.g., hydroxyethyl, chloroethyl).
- perfluoroalkyl groups are pentafluoroethyl and trifluoromethyl.
- antifogging agents according to this invention include the following. However, the scope of this invention is not limited to these compounds.
- the 3-mercapto-1,2,4-triazole for use in the present invention may be synthetized by methods well known in the art. Synthesis of compound 1 is described, for example, in US 4,447,454.
- the compounds represented by the general formula (I) may be added in any effective amount to the photographic emulsion.
- concentration of said compounds can vary significantly in photographic emulsions. A generally useful range would be from 0.1 to 1.0 mmoles per mol of silver. A more preferred range would be from 0.3 to 0.8 mmoles per mol of silver.
- the compounds can be directly dispersed in the photographic emulsion, or may be dissolved in a suitable solvent (e.g., water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or in a mixture of these solvents and added as a solution to the emulsion.
- a suitable solvent e.g., water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.
- said compounds can be added to the emulsion as a solution or as a colloid dispersion according to the processes for adding sensitizing dyes, as known to those skilled in the art.
- the infrared sensitive color photographic element of the present invention contains at least a supersensitizing agent.
- it is an 1-aryl-5-mercaptotetrazole compound substituted in the aryl group by at least one electron-attracting group as described in EP 440,947.
- the supersensitizing agent is an 1-aryl-5-mercaptotetrazole represented by the structural formula (II): wherein Ar is an aryl group bearing at least one electron-attracting group.
- the aryl group is a phenyl group and the electron-attracting groups are selected from the group consisting of nitro, cyano, fluoroalkyl, halogen (preferably, chlorine or bromine), carbamoyl (preferably, a C 1 to C 4 straight or branched alkylaminocarbonyl or an un-substituted or substituted phenylaminocarbonyl group), sulfamoyl (preferably, a C 1 to C 4 straight or branched alkylaminosulfonyl or an un-substituted or substituted phenylaminosulfonyl group), acylamino (preferably, a C 1 to C 4 straight or branched alkylcarbonamido or an unsubstituted or substituted phenylcarbonamido group), sulfonamido (preferably, a C 1 to C 4 straight or branched alkylsulfonamido or an unsubstituted or substituted
- the compounds of the present invention are represented by the structural formula (II) wherein Ar is a phenyl group bearing one or more C 1 to C 4 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 fluorine atoms.
- 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, 2-cyano-4-methylsulfonylphenyl group, 2,4-dinitrophenyl group, 2,4,6-tricyanophenyl group, 2-nitro-4-N,N-dimethylcarbamoylphenyl 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
- the compounds represented by the general formula (II) may be added in any effective stabilizing amount to the photographic emulsion.
- concentration of said compounds can vary significantly in photographic 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 compounds can be directly dispersed in the photographic emulsion, or may be dissolved in a suitable solvent (e.g., water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or in a mixture of these solvents and added as a solution to the emulsion.
- a suitable solvent e.g., water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.
- said compounds can be added to the emulsion as a solution or as a colloid dispersion according to the processes for adding sensitizing dyes, as known to those skilled in the art.
- any spectral sensitizing dye known to sensitize silver halide emulsions to infrared portion of the electromagnetic spectrum may be used in the practice of the present invention.
- the infrared portion of the electromagnetic 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 electromagnetic spectrum (e.g., about 750-780 nm).
- Useful dyes for this purpose tend to be merocyanines, cyanines and especially tricarbocyanines.
- Such dye sensitizers for the infrared are described for example in US Pat. Nos.
- the preferred classes of dyes are the tricarbocyanines such as 3,3'-dialkylthiatricarbocyanines, thiatricarbocyanines (especially with rigidified chains), selenotricarbocyanines, and enamine tricarbocyanines.
- Preferred classes of dyes are represented by the following general formula (III) or (IV): wherein:
- the present invention refers to dyes of the type above indicated in which both heterocyclic nuclei are of the benzothiazole series.
- R 5 and R 6 each represent a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms such as a methyl group or an ethyl group;
- R 7 represents a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 5 carbon atoms, an unsubstituted or substituted aryl group, an acyloxy group shown by wherein R 8 represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group.
- the infrared sensitizing dyes used in the present invention are incorporated in the silver halide photographic emulsion in a content of 5x10 -7 mol to 5x10 -3 mol, preferably 1x10 -6 mol to 1x10 -3 mol, more preferably 2x10 -6 mol to 5x10 -4 mol, per mol of silver within the particular layer which is being sensitized by that dye.
- the sensitizing dyes for use in the present invention can be prepared according to well-known procedures in the art, such those described in James, The Theory of Photographic Processes , MacMillan, 4th Edition, 1977, in US Pat. Nos. 2,734,900, 3,148,187, 2,895,955 and 3,423,207, in CA 56 114571 and J.Org.Chem., Vol 42, 1977, page 885. Synthetic techniques are also described by Y.L.Slominskii et al, UKR. Khim. Zh., 40, pages 625-629, 1974 and Zh.Org.Khim., 15, page 400, 1979. Preparation processes of such dyes are illustrated in the examples herein below. Variations in the structures of the final dyes may be made by the appropriate selection of reagents and the use of these varied methods.
- the infrared sensitizing dyes to be used in the present invention can be directly dispersed in the emulsion. 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.
- a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixture thereof.
- Processes 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 3,429,835.
- the aforesaid infrared sensitizing dyes may be uniformly dispersed in the silver halide emulsion before coating on a suitable support.
- this dispersing procedure may be conducted in any suitable step of preparing the silver halide emulsion.
- Infrared sensitive silver halide color photographic elements for use in the present invention are preferably those described in US 4,619,892, which is incorporated 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 infrared 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 described in said US 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 mixtures thereof may be used, for example, dispersed in a hydrophilic colloid or carrier. Any configuration of grains, cubic, orthorombic, hexagonal, 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 hardeners.
- Such hardeners are free aldehydes, aldehyde releasing compounds, 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 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, 2,236,598, 2,950,970, 2,592,243, 2,343,703, 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.
- dye image formers such as color couplers
- the developer contains a color developing agent (e.g., a primary aromatic amine which in its oxidized form is capable of reacting with the coupler to form the image dye).
- a color developing agent e.g., a primary aromatic amine which in its oxidized form is capable of reacting with the coupler to form the image dye.
- instant self-developing diffusion transfer film can be used as well as photothermographic color film or paper using silver halide in catalytic proximity 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, 2,269,158, 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 incorporated in different amounts to achieve differing photographic effects.
- GB 923,045 and US 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 ketomethylene, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, phenol and naphthol type hydrophobically ballasted for incorporation in high-boiling organic (coupler) solvents.
- Such couplers are illustrated in US Pat. Nos.
- the dye-forming couplers upon coupling can release photo-graphically useful fragments, such as development inhibitors or accelerators, bleach accelerators, developing agents, silver halide sol-vents, 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, 3,615,506, 3,265,506, 3,620,745, 3,632,345, 3,869,291, 3,642,485, 3,770,436, 3,808,945, and in GB Pat. Nos.
- DIR compounds which 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 relatively light insensitive, such as Lippmann emulsions, having been used as interlayers or overcoat layers to prevent or control the migration of development inhibitor fragments as described in US 3,892,572 can be employed.
- the photographic elements can incorporate colored dye-forming couplers, such as those employed to form integral 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 competing 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.
- colored dye-forming couplers such as those employed to form integral 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 competing 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.
- the color provided in the image produced by exposure of each of the differently 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.
- the commercially available color image forming mechanisms are the diffusion transfer of dyes, dye-bleaching, and leuco dye oxidation. Each of these procedures is used in commercial products, is well understood by the ordinary skilled photographic artisan, and is used with silver halide emulsions. Multicolor elements using these different technologies are also commercially available.
- the photographic elements can include image dye stabilizers.
- 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 1,326,889.
- Filter dyes can be included in the photographic elements. 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 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 elements.
- Dyes which will not allow transmission of radiation having wavelengths shorter than the shortest wavelength to which one of the emulsion layers 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 example) or leachable (e.g., removed by solvent action of any baths).
- photographic addenda such as coating aids, antistatic agents, acutance dyes, antihalation dyes and layers, antifoggants, latent image stabilizers, supersentizers, antikinking agents, high intensity reciprocity failure reducers, and the like may also be present.
- an AgCl emulsion having 0.45 ⁇ m average grain size, 9.1% Ag and 5.47% gelatin
- 291 g of an oil in water dispersion containing 65 g of coupler M 0.295 g of compound A, 3.31 g. of compound B and 8.73 g. of gelatin.
- the composition was diluted with 227 ml of water and added with 3% of gelatin.
- 0.2 mmole/mole Ag of spectral sensitizing dye SD, 0.96 mmole/mole Ag of supersensitizer ST, and 0.75 mmole/mole Ag of supersensitizer SS were added in the order to the composition.
- the composition was then maintained at 38°C for 40 minutes.
- the composition was coated onto a conventional photographic paper base at a coverage of 0.28 g/m 2 .
- the photosensitive layer was overcoated with a protective layer comprising gelatin, a surfactant and a vinylsulfonyl hardener.
- Sample 2 was prepared as Sample 1, but the stabilizer agent ST was added in an amount of 0.644 mmoles/mole Ag.
- Sample 3 was prepared as Sample 1, but the antifogging agent C was added in an amount of 0.282 mmoles/mole Ag.
- Sample 4 was prepared as Sample 2, but the antifogging agent C was added in an amount of 0.564 mmoles/mole Ag.
- Sample 5 was prepared as Sample 1, but the antifogging agent (I.1) of the present invention was added in an amount of 0.295 mmoles/mole Ag.
- Sample 6 was prepared as Sample 2, but the antifogging agent (I.1) of the present invention was added in an amount of 0.590 mmoles/mole Ag.
- Sample 7 was prepared as Sample 1, but the antifogging agent (I.2) of the present invention was added in an amount of 0.337 mmoles/mole Ag.
- Sample 8 was prepared as Sample 2, but the antifogging agent (I.2) of the present invention was added in an amount of 0.675 mmoles/mole Ag.
- Sample 9 was prepared as Sample 1, but the antifogging agent D was added in an amount of 0.304 mmoles/mole Ag.
- Sample 10 was prepared as Sample 2, but the antifogging agent D was added in an amount of 0.608 mmoles/mole Ag.
- Sample 11 was prepared as Sample 1, but the antifogging agent E was added in an amount of 0.348 mmoles/mole Ag.
- Sample 12 was prepared as Sample 2, but the antifogging agent E was added in an amount of 0.697 mmoles/mole Ag.
- Table 1 shows that the sensitometric values obtained by samples 1 and 2, not containing any antifogging agents, present a high Dmin.
- Samples 5 to 8 of the present invention present results (low Dmin and high speed) comparable with those of reference samples 3 and 4, even if antifogging agents I.1 and I.2 have substituents with less than 3 carbon atoms.
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Description
Antifog | Amount | Dmin | Speed | |
1. | -- | -- | 0.22 | 235 |
2. | -- | -- | 0.17 | 218 |
3. (ref.) | C | 0.282 | 0.12 | 216 |
4. (ref.) | C | 0.564 | 0.11 | 195 |
5. (inv.) | I.1 | 0.295 | 0.13 | 215 |
6. (inv.) | I.1 | 0.590 | 0.10 | 191 |
7. (inv.) | I.2 | 0.337 | 0.12 | 211 |
8. (inv.) | I.2 | 0.675 | 0.11 | 190 |
9. | D | 0.304 | 0.18 | 221 |
10. | D | 0.608 | 0.10 | 178 |
11. | E | 0.348 | 0.23 | 195 |
12. | E | 0.697 | * | * |
(*) Sample completely fogged |
Claims (8)
- A silver halide photographic element comprising a support and at least one silver halide emulsion layer spectrally sensitized to the infrared portion of the electromagnetic spectrum, characterized in that said infrared sensitized emulsion layer is associated with a 3-mercapto-1,2,4-triazole antifogging agent represented by the formula : wherein R1 and R2 each independently represents hydrogen or an alkyl group, the sum of carbon atoms of R1 and R2 is 1 or 2, and at least one of R1 and R2 is a perfluoroalkyl group.
- The silver halide photographic element of claim 1 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 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, characterized in that at least one of said infrared sensitized emulsion layer is associated with said 3-mercapto-1,2,4-triazole antifogging agent.
- The silver halide photographic element of claim 1, wherein 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.
- The photographic element of claim 3 wherein the aryl group is a phenyl group.
- The photographic element of claim 3 wherein the electron-attracting group is selected from the group consisting of nitro, cyano, fluoroalkyl, halogen, carbamoyl, sulfamoyl, acylamino, sulfonamido and acyl.
- The photographic element of claim 1 wherein the 3-mercapto-1,2,4-triazole is present in an amount from about 0.1 mmoles/mole silver to about 1.0 mmoles/mole silver halide.
- The photographic element of claim 1 wherein said silver halide emulsion is sensitized by a dye selected form the class consisting of thia-, benzothia-, seleno-, benzoseleno-, imida-, benzoimida-, oxa-, benzoxa-, and enamine tricarbocyanines.
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US4910129A (en) * | 1987-04-17 | 1990-03-20 | Mitsubishi Paper Mills, Ltd. | Silver halide photographic light sensitive material |
DE58907613D1 (en) * | 1988-11-15 | 1994-06-09 | Agfa Gevaert Ag | Silver halide recording material. |
US5149620A (en) * | 1990-07-30 | 1992-09-22 | Minnesota Mining And Manufacturing Company | Post processing stabilized photothermographic emulsions |
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