US3718475A - Silver halide supersensitized photographic emulsion - Google Patents
Silver halide supersensitized photographic emulsion Download PDFInfo
- Publication number
- US3718475A US3718475A US00049981A US3718475DA US3718475A US 3718475 A US3718475 A US 3718475A US 00049981 A US00049981 A US 00049981A US 3718475D A US3718475D A US 3718475DA US 3718475 A US3718475 A US 3718475A
- Authority
- US
- United States
- Prior art keywords
- group
- silver halide
- halide emulsion
- emulsion
- sensitizing dyes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 104
- -1 Silver halide Chemical class 0.000 title claims abstract description 90
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 76
- 239000004332 silver Substances 0.000 title claims abstract description 76
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000000975 dye Substances 0.000 claims description 72
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims description 12
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 206010034960 Photophobia Diseases 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 208000013469 light sensitivity Diseases 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 claims 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 229910052740 iodine Inorganic materials 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000003595 spectral effect Effects 0.000 description 11
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 150000001556 benzimidazoles Chemical class 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000004964 sulfoalkyl group Chemical group 0.000 description 3
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical class C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 2
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 2
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical class C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- AGJZCWVTGOVGBS-UHFFFAOYSA-N 1,1'-diethyl-2,2'-cyanine Chemical compound C1=CC2=CC=CC=C2N(CC)\C1=C\C1=CC=C(C=CC=C2)C2=[N+]1CC AGJZCWVTGOVGBS-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- 101100001642 Caenorhabditis elegans amt-1 gene Proteins 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101100114416 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) con-10 gene Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000003960 organic solvent Substances 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
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000004950 trifluoroalkyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 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
- G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
Definitions
- ABSTRACT A silver halide photographic emulsion is super-sensitized in the green wave length region by adding thereto at least one sensitizing dye of the following formula I and at least one sensitizing dye of the following formula ll; and, optionally a compound of the following formula III:
- This invention relates to a super-sensitized silver halide photographic emulsion and more particularly it relates to -a supersensitized silver halide photographic emulsion for increasing particularly the spectral senl emulsion containing couplers for making color photographic light-sensitive materials.
- a spectral sensitizing method is one of the techniques employed in the manufacture of silver halide photographic emulsions, and that the sensitizing method is an indispensible technique for the production of color photographic light-sensitive materials.
- the spectral sensitivity obtained by the method is influenced not only by the chemical structure of the sensitizing dye to be used and the properties of the silver halide emulsion to be used, such as the composition of the halogen and the crystal system ofthe silver halide contained in the emulsion, the manner of chemical ripening, the silver ion concentration and the hydrogen ion concentration of the emulsion, but also by the various kinds of additives added to the silver halide emulsion.
- the spectral sensitivity is reduced.
- a certain kind of sensitizing dye is used together with a dye or a colorless aromatic compound having a specific chemical structure according to the chemical structure and the properties of the sensitizing dye, a higher spectral sensitivity is obtained than when using each of the sensitizing dyes alone. This is known as a super-sensitizing action.
- silver halide emulsions used for producing color photographic light-sensitive materials contain a large amount of couplers, and when a coupler is incorporated in a silver halide photographic emulsion containing a sensitizing dye, the spectral sensitivity becomes lower than the spectral sensitivity obtained by using the sensitizing dye alone.
- the presence of the coupler reduces the super-sensitizing action.
- the spectral sensitivity distribution in the green region is one of the most important factors for the color reproduction of color photographic light-sensitive materials and for the quality of the image obtained.
- a primary object of the present invention is to provide a silver halide photographic emulsion having both a high spectral sensitivity in a wave length region of 500-530 my. and less of a contamination by the dyes after development.
- Another object of the present invention is to provide a silver halide photographic emulsion used for producing a color photographic light-sensitive material having a high green sensitivity in the presence of a coupler.
- R and R each represent an alkyl group, an aryl group or a substituted alkyl group
- R and R each represent an alkyl group, an aryl group or a substituted alkyl group (including a substituted alkyl group having a sulfo group); at least one of said R and R being a substituted alkyl group having a sulfo group
- Z and Z (which may be same or different) eachrepresents a non-metallic atomic group necessary to complete a heterocyclic nucleus of the benzimidazole series
- X,- represents an acid anion group usually employed in cyanine dyes
- p is an integer of 1 or 2, p being 1 when the cyanine dye of formula I forms an intermolecular salt
- Z represents a non-metallic atomic group necessary to complete a heterocyclic nucleus of the 2- quinoline series
- Z represents a non-metallic atomic group necessary to complete a benzoxazole nucleus, a naphthoxazole nucleus, a benzthiazole nucleus, a benzselenazole nucleus, a naphthothiazole nucleus, or a naphthoselenazole nucleus, each being unsubstituted or substituted by an alkyl group, a phenyl group, a halogen atom, an alkoxyl group or an alkoxyl group having a sulfo group; R and R, (which may be same or different) each represents an alkyl group or a substituted alkyl group (including a substituted alkyl group having a sulfo group); at least one of said R and R being a
- the substituted alkyl group of R in the above-men- is, for example, a sulfoalkyl group present invention that a particularly better result is obneutralized by a cation, such as alkali metal ions, ortained by incorporating a compound represented by ganic ammonium ions, a pyridinium ion, a benzylthiouthe following formula III in the above-mentioned silver m ronium ion, and the like, usually employed in cyanine halide photographic emulsion: dyes, a cyanoalkyl group and an allyl group.
- a cation such as alkali metal ions
- X and X in the formulas I and II there maybe il- FORMULA In lustrated, e.g., a halogen, perchlorate, thiocyanate, ptoluene sulfonate, benzene sulfonate, methyl sulfate and ethyl sulfate ions.
- the sensitizing dye represented by formula II has at 7 least one sulfo group in the heterocyclic nucleus conwherein R represents an alkyl group or a substituted taimng R5 or '.T Spectral sensltlzanon 0balkyl group; Z represents a non-metallic atomic group gamed by 1 .sensmzmg dye rePresemed.
- Z represents a phenyl group sulfo group but.when the sensmzmg y represented by the formula I 15 used together therewith, the spectral or a substituted phenyl group, such as a phenyl group sensitization is increased substituted by alkyl groups, alkoxy groups, and the like.
- a p y EMBODIMENTS group a halogen atom, an alkoxyl group, or an alkoxyl group substituted by at least a sulfo group; in other
- the substituent is so selected that the maximum groups of R1 to R6 f methyl ethyl "'P sensitivity obtained by using at least one sensitizing dye Pf and lso'butyl groups; and as the of formula II and at least one compound of formula I in smuted alkyl groups of 1 to e there y be combination does not shift to a longer wavelength side "med: y group, aralkyl group, a l y' than that of the sensitizing dye of formula II.
- the compound represented by formula III shows a YP Py p a B' y y group, a Y- super-sensitizing action to the sensitizing dye sulfatopropyl group, a s'sulfatobutyl group, a represented by formula I and to the sensitizing dye acetylsulfamyl g p and a B y y Y 8 "P- represented by formula II, and by using the compound
- t e e may be illust ated a fi-sulf p opyl tion of the other two sensitizing dyes, the green seng p, fiy g p.
- a 5-Sulf0buty1 g p. 3 40 sitivity is further increased and at the same time the p p y) y g p, a p p xsensitivity in the wave length region of 500-530 MA, y) yl y g p, d a Z-hydroxy-l-sulfopropyl which is present at a shorter wave length side of the S P' green region, is further increased.
- benzimidazole series nucleus completed by The compounds which may be used in the present in- Z,, Z, or 2,, there may be illustrated: benzimidazole vention will be further illustrated by reference to the and benzimidazole containing, as a component of the following illustrative formulas, which are merely illusskeletal-structure thereof, a benzene ring substituted trative, and not limiting, in nature.
- a halogen atom an N- unsubstituted or alkyl substituted sulfamyl or carbamyl (IA) 0 H C H group
- an N-disubstituted sulfamyl group such as a Cl 2 5 5 morpholino sulfonyl group, an alkyl sulfonyl group, a trifluoromethyl group
- sensitizing dyes and the compounds used in this invention which were not described above, may also be easily synthesized by referring to the specifications of the above patents.
- the compounds used in this invention are incorporated in a sliver halide emulsion as solutions in water or a water-soluble organic solvent such as methanol, ethanol, and pyridine.
- the sensitizing dyes represented by formulal and formula 11, respectively, may be added to a silver halide emulsion as a mixture of the solutions thereof or as separate solutions. The amounts of these dyes are greatly influenced by the nature of the silver halide emulsion to be used.
- the total amount of the above-mentioned sensitizing dyes (1 and 11) and compound 111 are preferably from 1 X mol to 1 X 10 mol, per mol of silver halide.
- the weight ratio of the amount of the sensitizing dye represented by formula II to the amount of the sensitizing dye represented by formula I is preferably from 10:1 to 1:2, but this ratio is varied by the amount of the compound represented by formula III to be added.
- the silver halide emulsion which may be used in this invention, there may be illustrated: a silver iodobromide emulsion, a silver bromide emulsion, a silver chlorobromide emulsion, etc.
- the silver halide emulsion used in this invention is mainly a gelatino silver halide emulsion but the emulsion may contain, besides gelatin, polyvinyl alcohol, an alginic acid polymer, polyvinyl imidazole, polyvinyl pyrrolidone, or copolymers thereof, or may be an emulsion thereof.
- the silver halide emulsion of this invention is applied to a suitable support according to the desired use, such as a paper, a glass plate, a cellulose triacetate film, a polyethylene terephthalate film, other plastic films than above, a baryta-coated paper, a resin-coated paper, or a synthetic paper.
- a suitable support such as a paper, a glass plate, a cellulose triacetate film, a polyethylene terephthalate film, other plastic films than above, a baryta-coated paper, a resin-coated paper, or a synthetic paper.
- EXAMPLE 1 50 g of l-pheny1-3-[3-(2,4-di-tertiaryamylphenoxyactamido)-benzamido]S-pyrazolone was dissolved in 100 ml of dibutyl phthalate by heating and the resultant solution was added to 1 liter of a 10 percent aqueous gelatin solution. Then, 50 ml of a 5 percent aqueous solution of sodium alkylbenzene sulfonate was added thereto and they were dispersed by emulsification by means of a high speed rotary mixer (the product is called the dispersion of the magenta coupler).
- the dispersion of the magenta coupler as prepared above was added to the emulsion with stirring and after adding further suitable amounts of a hardening agent and an ampholite surface active agent as a wetting agent to the mixture with stirring, the resultant mixture was applied to a cellulose triacetate film in a thickness of 7 microns to obtain a sample of a green-sensitive light-sensitive material.
- the sample was cut into strips and subjected to an optical wedge exposure through Yellow Filter No. K-12 made by Fuji Photo Film Co. by using a sensitometer of 5400K in color temperature of the light source.
- the strip thus exposed was developed for 12 minutes at C in a color developer having the following composition:
- compositions of the bleaching solution and the fixing solution used in the above processing were as follows:
- EXAMPLE 2 As in Example 1, 1 kg of a silver iodobromide emulsion (containing 0.30 mol of silver and 6.0 mol% of iodine) was melted in a beaker at 40C and the amounts of the sensitizing dyes l and II and the compound of formula III shown in Table 2 were added to the emulsion with stirring. -7 ml of the silver halide emulsion thus obtained was applied to a glass plate of cabinet size followed by drying to obtain a sample.
- the sample was cut into strips and the strips were subjected to an optical wedge exposure by yellow light as in Example 1 and then developed in a developer having the following composition for 10 minutes at C.
- R 1 l substituent being alkyl, halogen, trifluoroalkyl, cyano, alkyl-sulfonyl, alkylsulfomyl or alkylcarbamyl; and at least one sensitizing dye represented by the following second formula:
- R is alkyl or sulfoalkyl
- R is alkyl, sulfoalkyl, sulfoalkoxyalkoxy or sulfoalkylcarbamylalkyl
- Z represents a non-metallic atomic group necessary to complete a Z-quinoline substituted or unsubstituted heterocyclic nucleus, the substituent being alkyl or halogen
- Z represents a non-metallic group necessary to complete a substituted or unsubstituted heterocyclic nucleus selected from the group consisting of benzoxazole, naphthoxazole, benzthiazole, benzselenazole, naphthothiazole or naphthoselenazole, the substituent being halogen or sulfoalkoxy; with the proviso that when Z contains a sulfoalkoxy group, R and R is alkyl.
- R represents an alkyl group or a substituted alkyl group wherein the substituent is a sulfo group neutralized by a cation, a cyano group or a vinyl group
- Z represents an atomic group necessary to complete a heterocyclic nucleus of the benzimidazole series
- Z represents a phenyl group or a substituted phenyl group wherein the substituent is alkyl or alkoxy.
- heterocyclic nucleus of the 2-quinoline series is a 2-quinoline nucleus or a 2-quinoline nucleus 5 containing, as a component of the skeletal-structure thereof, a benzene ring substituted by at least one of 11915011 the groups consisting of an alkyl group and a halogen (31W atom.
- a silver halide emulsion according to claim 11 ⁇ V *CHZC CzHrNHC OCaHaSOa' and a compound of the following formula:
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP44050117A JPS4838406B1 (enrdf_load_stackoverflow) | 1969-06-25 | 1969-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3718475A true US3718475A (en) | 1973-02-27 |
Family
ID=12850150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00049981A Expired - Lifetime US3718475A (en) | 1969-06-25 | 1970-06-25 | Silver halide supersensitized photographic emulsion |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3718475A (enrdf_load_stackoverflow) |
| JP (1) | JPS4838406B1 (enrdf_load_stackoverflow) |
| BE (1) | BE752386A (enrdf_load_stackoverflow) |
| DE (1) | DE2031491A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2052878A5 (enrdf_load_stackoverflow) |
| GB (1) | GB1293862A (enrdf_load_stackoverflow) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3765899A (en) * | 1969-03-14 | 1973-10-16 | Konishiroku Photo Ind | Light-sensitive super-sensitized silver halide photographic emulsion |
| US3849147A (en) * | 1969-06-25 | 1974-11-19 | Fuji Photo Film Co Ltd | Silver halide supersensitized photographic emulsion |
| US3856532A (en) * | 1972-04-26 | 1974-12-24 | Ilford Ltd | Photographic silver halide emulsion containing a supersensitising combination |
| US3933510A (en) * | 1972-09-04 | 1976-01-20 | Fuji Photo Film Co., Ltd. | Spectrally sensitized silver halide photographic emulsion |
| USH899H (en) | 1986-03-25 | 1991-03-05 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material feasible for high speed |
| US5091298A (en) * | 1990-07-19 | 1992-02-25 | Eastman Kodak Company | Sensitizing dyes for photographic materials |
| US5389505A (en) * | 1992-09-18 | 1995-02-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| US5478720A (en) * | 1993-04-01 | 1995-12-26 | Konica Corporation | Silver halide photographic emulsion and silver halide photographic light-sensitive material |
| US5523203A (en) * | 1993-03-03 | 1996-06-04 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| US5610005A (en) * | 1993-11-25 | 1997-03-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
| US6479226B2 (en) * | 2000-04-27 | 2002-11-12 | Konica Corporation | Silver halide color photographic light sensitive material |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59188641A (ja) | 1983-04-11 | 1984-10-26 | Fuji Photo Film Co Ltd | ハロゲン化銀写真乳剤 |
| JPS61245151A (ja) | 1985-04-23 | 1986-10-31 | Konishiroku Photo Ind Co Ltd | ハロゲン化銀写真感光材料 |
| JPS61251852A (ja) | 1985-04-30 | 1986-11-08 | Konishiroku Photo Ind Co Ltd | ハロゲン化銀カラ−写真感光材料の処理方法 |
| JPS61250643A (ja) | 1985-04-30 | 1986-11-07 | Konishiroku Photo Ind Co Ltd | ハロゲン化銀写真感光材料 |
| US4725529A (en) | 1985-04-30 | 1988-02-16 | Konishiroku Photo Industry Co., Ltd. | Developing inhibitor arrangment in light-sensitive silver halide color photographic materials |
| JPS61250645A (ja) | 1985-04-30 | 1986-11-07 | Konishiroku Photo Ind Co Ltd | ハロゲン化銀写真感光材料 |
| AU590563B2 (en) | 1985-05-16 | 1989-11-09 | Konishiroku Photo Industry Co., Ltd. | Method for color-developing a silver halide color photographic light-sensitive material |
| DE3682128D1 (de) | 1985-07-17 | 1991-11-28 | Konishiroku Photo Ind | Photographisches silberhalogenidmaterial. |
| AU591540B2 (en) | 1985-12-28 | 1989-12-07 | Konishiroku Photo Industry Co., Ltd. | Method of processing light-sensitive silver halide color photographic material |
| EP0476327B1 (en) | 1990-08-20 | 1999-11-17 | Fuji Photo Film Co., Ltd. | Data-retainable photographic film product and process for producing color print |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2533427A (en) * | 1949-07-13 | 1950-12-12 | Eastman Kodak Co | Supersensitization of meso-aryl carbocyanine dyes |
| US2541400A (en) * | 1944-11-11 | 1951-02-13 | Eastman Kodak Co | N, n'-alkylenecyanine dyes |
| US2701198A (en) * | 1954-02-16 | 1955-02-01 | Eastman Kodak Co | Supersensitized photographic emulsions containing simple cyanine dyes |
| US3038800A (en) * | 1957-12-19 | 1962-06-12 | Eastman Kodak Co | Photopolymerization of olefinicallyunsaturated monomers by silver halides |
-
1969
- 1969-06-25 JP JP44050117A patent/JPS4838406B1/ja active Pending
-
1970
- 1970-06-23 BE BE752386D patent/BE752386A/xx unknown
- 1970-06-23 FR FR7023203A patent/FR2052878A5/fr not_active Expired
- 1970-06-24 GB GB30696/70A patent/GB1293862A/en not_active Expired
- 1970-06-25 DE DE19702031491 patent/DE2031491A1/de active Pending
- 1970-06-25 US US00049981A patent/US3718475A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2541400A (en) * | 1944-11-11 | 1951-02-13 | Eastman Kodak Co | N, n'-alkylenecyanine dyes |
| US2533427A (en) * | 1949-07-13 | 1950-12-12 | Eastman Kodak Co | Supersensitization of meso-aryl carbocyanine dyes |
| US2701198A (en) * | 1954-02-16 | 1955-02-01 | Eastman Kodak Co | Supersensitized photographic emulsions containing simple cyanine dyes |
| US3038800A (en) * | 1957-12-19 | 1962-06-12 | Eastman Kodak Co | Photopolymerization of olefinicallyunsaturated monomers by silver halides |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3765899A (en) * | 1969-03-14 | 1973-10-16 | Konishiroku Photo Ind | Light-sensitive super-sensitized silver halide photographic emulsion |
| US3849147A (en) * | 1969-06-25 | 1974-11-19 | Fuji Photo Film Co Ltd | Silver halide supersensitized photographic emulsion |
| US3856532A (en) * | 1972-04-26 | 1974-12-24 | Ilford Ltd | Photographic silver halide emulsion containing a supersensitising combination |
| US3933510A (en) * | 1972-09-04 | 1976-01-20 | Fuji Photo Film Co., Ltd. | Spectrally sensitized silver halide photographic emulsion |
| USH899H (en) | 1986-03-25 | 1991-03-05 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material feasible for high speed |
| US5091298A (en) * | 1990-07-19 | 1992-02-25 | Eastman Kodak Company | Sensitizing dyes for photographic materials |
| US5389505A (en) * | 1992-09-18 | 1995-02-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| US5523203A (en) * | 1993-03-03 | 1996-06-04 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| US5478720A (en) * | 1993-04-01 | 1995-12-26 | Konica Corporation | Silver halide photographic emulsion and silver halide photographic light-sensitive material |
| US5610005A (en) * | 1993-11-25 | 1997-03-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
| US6479226B2 (en) * | 2000-04-27 | 2002-11-12 | Konica Corporation | Silver halide color photographic light sensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| BE752386A (fr) | 1970-12-01 |
| DE2031491A1 (de) | 1971-01-28 |
| FR2052878A5 (enrdf_load_stackoverflow) | 1971-04-09 |
| JPS4838406B1 (enrdf_load_stackoverflow) | 1973-11-17 |
| GB1293862A (en) | 1972-10-25 |
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