US3649288A - Supersensitized silver halide photographic emulsion - Google Patents
Supersensitized silver halide photographic emulsion Download PDFInfo
- Publication number
- US3649288A US3649288A US56959A US3649288DA US3649288A US 3649288 A US3649288 A US 3649288A US 56959 A US56959 A US 56959A US 3649288D A US3649288D A US 3649288DA US 3649288 A US3649288 A US 3649288A
- Authority
- US
- United States
- Prior art keywords
- group
- silver halide
- halide emulsion
- photographic silver
- alkyl
- 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 abstract description 142
- 239000000839 emulsion Substances 0.000 title claims abstract description 77
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 54
- 239000004332 silver Substances 0.000 title claims abstract description 54
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000004442 acylamino group Chemical group 0.000 claims description 4
- 125000001769 aryl amino group Chemical group 0.000 claims description 4
- 125000004964 sulfoalkyl group Chemical group 0.000 claims description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000005184 naphthylamino group Chemical group C1(=CC=CC2=CC=CC=C12)N* 0.000 claims description 3
- 125000005936 piperidyl group Chemical group 0.000 claims description 3
- 125000004149 thio group Chemical group *S* 0.000 claims description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000005191 hydroxyalkylamino group Chemical group 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 4
- 125000002373 5 membered heterocyclic group Chemical group 0.000 abstract description 2
- 125000004070 6 membered heterocyclic group Chemical group 0.000 abstract description 2
- 125000000547 substituted alkyl group Chemical group 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 37
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 2
- 125000004429 atom 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
- 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
- 239000000460 chlorine Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- 150000003549 thiazolines Chemical class 0.000 description 2
- JEOQACOXAOEPLX-WCCKRBBISA-N (2s)-2-amino-5-(diaminomethylideneamino)pentanoic acid;1,3-thiazolidine-4-carboxylic acid Chemical compound OC(=O)C1CSCN1.OC(=O)[C@@H](N)CCCN=C(N)N JEOQACOXAOEPLX-WCCKRBBISA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GAGVTQRAYMKUMR-UHFFFAOYSA-N 1,2,3a,4-tetrahydrobenzo[e][1,3]benzothiazole Chemical class C1=CC=CC2=CCC(SCN3)C3=C21 GAGVTQRAYMKUMR-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- UUJOCRCAIOAPFK-UHFFFAOYSA-N 1,3-benzoselenazol-5-ol Chemical compound OC1=CC=C2[se]C=NC2=C1 UUJOCRCAIOAPFK-UHFFFAOYSA-N 0.000 description 1
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- GAOGPNYSGYFOHS-UHFFFAOYSA-N 2-chloro-1,3-benzoselenazole Chemical compound C1=CC=C2[se]C(Cl)=NC2=C1 GAOGPNYSGYFOHS-UHFFFAOYSA-N 0.000 description 1
- BJATXNRFAXUVCU-UHFFFAOYSA-N 4-methyl-1,3-selenazole Chemical compound CC1=C[se]C=N1 BJATXNRFAXUVCU-UHFFFAOYSA-N 0.000 description 1
- SRGCYOMCADXFJA-UHFFFAOYSA-N 4-methyl-4,5-dihydro-1,3-thiazole Chemical compound CC1CSC=N1 SRGCYOMCADXFJA-UHFFFAOYSA-N 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
- MLBGDGWUZBTFHT-UHFFFAOYSA-N 4-phenyl-1,3-selenazole Chemical compound [se]1C=NC(C=2C=CC=CC=2)=C1 MLBGDGWUZBTFHT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 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
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000005110 aryl thio 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
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 238000005406 washing Methods 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
Definitions
- ABSTRACT A supersensitized silver halide emulsion comprising a sensitizing dye of the general formula [l] O 1J3 Il1 --Zi atom or an alkyl or an aryl group m, n and p each represents 7 1 or 2 and d represents 0, 1 or 2; X- represents an anion and forms an intramolecular salt when p is 1; and Z and Z which may be same or different, each represents the nonmetallic atomic groups necessary to complete a 5- or 6- membered heterocyclic nucleus and a polycyclic aromatic sulfo compound of the general formula [II] Ds a [In wherein M represents
- EMULSION each represents a group of the alkyl series, i.e., an alkyl, a substituted alkyl, or an allyl aralkyl group;
- L represents a BACKGROUND OF THE INVENTION monomethyne group or aliphatic hydrocarbon chain which Field Ofthe Invention 5 may combine with the N-atom in the heterocyclic ring con-
- This invention relates to a silver halide photographic emultammg 21 to form 3
- R4 represents a hydrogen atom or an sion.
- this invention relates to a so-called alkyl or an aryl group; n and P each rePresems l or 2 d supersensitized" silver halide photographic emulsion. represents 1 or 2; X Presents an amen and ffjrms an Description Ofthe Prior An tramolecular salt when p is l; and Z and 2,, which may be It is well known in the art ofthe manufacture ofsilver halide same or dlfferenn each represents the nonmetalhc atomlc photographic emulsions that the sensitive range of the spec- EYOUPS necessary to complete a or 'membered hetero trum of silver halide emulsion can be expanded, that is, the cycl'c nucleus" emulsion is spectrally sensitized by addition thereto of a sen- R and R3 m the general formula [I] a group m the sitizing dye or a Spectral Sensitizen
- the supersensitizabromme a Wrchlorate a p'Foluenesulfonate a tion Ofien causes a Shift in the Sensitization maximum. beneneksulfonate ion, an ethylsulfate ion, a methylsulfate ion ort e i e.
- the heterocyclic nucleus completed by the Z or Z in the general formula [I], for example, can be of the thiazole series,
- ad such as thiazole itself and thiazoles having a substituent on its dition to a silver halide photographic emulsion ofa sensitizing ring such as methyl or phenyl
- benzothiazole series dye represented by the following general formula [l] such as benzothiazole itself and benzothiazoles having ring wherein R, R,, R and R which may be same or different, substituents such as, for example, a halogen atom, an alkyl, an each represents a group of the alkyl series, i.e., an alkyl, a subalkoxyl or a phenyl group; of the naphthothiazole series, such stituted alkyl, or an allyl aralkyl
- the sensitizing dye is one represented by the benzimidazole series, such as l,3-dimethylbenzimidazole, the following general formula [I] l,3-diethylbenzimidazole, l,3-cliethyl-5-chlorobenzimidazole,
- M in the general formula [I] is, for example, a sodium ion, a potassium ion, an ammonium ion, a triethanolammonium ion aNd a pyridinium ion.
- the polycyclic aromatic compound having at least one sulfo group in the molecule used in combination with the sensitizing dye having the general formula [I] is of the general formula DSO;,M 111 wherein M represents a hydrogen atom or a cation forming a water-soluble salt of a compound represented by said formula [II], and D represents a polycyclic aromatic radical.
- polycyclic aromatic radical as used in the general formula lll] is intended to encompass a residue of a compound containing at least one condensed aromatic nucleus, such as, for example, a naphthalene or a purene nucleus or a residue of at least two benzene nuclei or other aromatic nuclei, such as, of a triazine, or a purimidine nucleus which are combined directly with each other such as, for example, diphenyl, terphenyl or quaterphenyl or through an aliphatic chain, an atom or an atomic group with each other".
- the sulfo-group-containing polycyclic aromatic compound of the general formula [II] will be hereinafter designated as sulfo compound" for convenience.
- spectral sensitizer represented by the general formula [I] (hereinafter dye) in a series of concentrations of the sensitizer, and to each is added the "sulfo compound" at various concentrations, for instance, concentrations of l, 5, l and 20 times the concentration of the dye.
- the so sensitized emulsions are separately applied to supports and dried.
- the photographic elements thus obtained are subjected to sensitometer testing for determination of the range and degree of spectral sensitivity of the emulsions.
- the sensitivity brought about by the combination of the dye and the sulfo compound exceeds, even if in a least a portion of the range of photosensitization, the sensitivity brought about by the dye alone at the same concentration of the combined concentration of the dye and the sulfo compound in the combination, this is the evidence for a supersensitization effect.
- sensitizing dyes of the general formula [I] for use in accordance with the present invention are disclosed by F.M. Hamer in C yam'n Dyes and Related Compounds, Chapter 15, p. 671, Interscience Publishers 1964).
- the sensitizing dye of the general formula [I] for use in the present invention is a dye containing at least four heterocyclic rings in which two ketomethylene nuclei are directly bonded to each other.
- the sensitizing dye of the general formula [I] differs from dyes containing one ketomethylene nucleus in the center of the molecule and the two basic nuclei and from trinuclear dyes containing two ketomethylene nuclei, not only in chemical structure but also in the following characteristics.
- the trinuclear dyes containing two ketomethylene nuclei in general have low solubilities in methanol, while the sensitizing dye represented by the general formula [I] has a high solubility in methanol or similar solvents.
- the sensitizing dye represented by the general formula [I] incorporated in a silver halide photographic emulsion imparts thereto a sensitivity which is reduced only slightly by the addition of conventional additives for photographic emulsions such as, for example, color couplers, antifogging agents and irradiation inhibiting dyes.
- the sensitizing dye represented by the general formula [I] when used alone, however, is generally inferior in sensitizing power to dyes. having one ketomethylene nucleus in the center of the molecule and two basic nuclei and needs another sensitizing technique to provide a highly sensitive emulsion. This additional sensitization is attained by the combination of the sensitizing dye represented by the general formula [I] with the sulfo compound.
- the incorporation of the sulfo compound represented by the general formula [II] in combination with the sensitizer represented by the general formula [I] in a silver halide emulsion results in supersensitization, and, according to the circumstances, a marked reduction of fog in comparison with the incorporation of the sensitizer alone.
- some of the sensitizing dyes represented by the general formula [I] have disadvantages in that they cause a reduction of the sensitivity of emulsion during storage when incorporated in photosensitive materials, the reduction in sensitivity during storage can be minimized by incorporating into the emulsion the sensitizer in combination with a certain one of the sulfo compounds represented by the general formula [il].
- the combination of the sensitizer of the general formula [I] and the sulfo compound of the general formula [II] has a super sensitization effect over a wide range of amounts added to a silver halide emulsion.
- the optimum amount of the sensitizer and of the sulfo compound to give the desired supersen sitization can be determined by conventional methods used in photographic emulsion techniques.
- the extent of the supersensitization can be determined by measuring the sensitivity using a spectral sensitometer.
- the sensitizer at a concentration of from 0.002 to 0.2 g./g.-mol of silver halide and the sulfo compound at a concentration of from 0.01 to l0.0 g./g.-rnol of silver halide in the silver halide emulsion.
- the preferred ratio of the concentration of the sensitizer to the concentration of the sulfo compound ranges from 1:1 to 1:200.
- Addition of the sensitizer to an emulsion can be performed in the conventional manner well known in the art.
- the sulfo compound can be added as a solution in water or in 21 methanol, ethanol or like organic solvent to a silver halide emulsion.
- sensitizer and the sulfo compound can be added to the emulsion before application to a substrate.
- the sensitizer and the sulfo compound can be added to the emulsion in the order of the sensitizer and then the sulfo compound or, alternately, the sulfo compound and then the sensitizer or they can be added in admixture to the emulsion.
- the incorporation of the sensitizer and the sulfo compound can also be attained during ageing of the photosensitive element after washing with water.
- the silver halide emulsion of the present invention there can be used, in place of gelatin in a gelatin-silver halide emulsion, resinous materials and derivatives having no adverse effects on photosensitive materials.
- silver chloride silver bromide, silver iodobromide, silver chloroiodide, silver chloroiodobromide and similar silver halides can be used.
- Chemical sensitizers, antifogging agents, stabilizers, hardeners, coating assistants, plasticizers, developing promoters, toners, fluorescent whitening agents, anti-airfogging agents, couplers and other conventional additives can be incorporated in the emulsion of the present invention.
- Dyes used in the silver-dye bleaching process as disclosed in Japanese Pat. specification No. 35/ 13093 can also be incorporated in the emulsion.
- the emulsion can be applied conventionally to a suitable support such as, for example, sheet glass, cellulose derivative films, synthetic resin films or baryta papers.
- the sensitizer of the general formula [I] for use in the present invention is exemplified by the following specific examples but is not limited thereto.
- the sulfo compounds of the general formula [II] for use in 11-4 the present invention are exemplified by the following com- N pounds but are not limited thereto. -l W 11-1 1 N N o Na Gyms C) The present invention is illustrated in greater detail by reference to the following examples but is not limited thereby.
- the value of the sensitivity is the relative value of the amount of exposure needed to give an optical density (including fog) of 0.l and was calculated by basing the relative sensitivity of an emulsion containing the sensitizer alone as 100.
- Additives (mg) l/ Milligrams ofadditive er gram mole ofsilvcr halide.
- each is selected from the group consisting of a group of the 3' figs- 13112323; :88 8-3; alkyl series; R is selected from the group consisting of a Mwi'l) I hydrogen atom, an alkyl group and an aryl group; wherein Z 1-4 95.1 ll-6(968) 155 0.05 and 2,, whlch ma be the same or d1fferent, each 15 the nong Y 14(951) 145 metall1c atom1c groups necessary to complete a heterocyclic 0 nucleus selected from the group consisting of the thiazole se- 3 ries, benzothiazole series, naphthothiazole series, oxazole sel-l(46.0) ll-8t968) 152 0.07 b 1 h h l l l Hugo) "8068) m r1 es, enzoxazo e senes, nap t ox
- At least one sulfo compound havmg the following general w l2(43.3) ii-ZO(484) I32 0.07 formula x l-2(48.3) 11-21mm) 152 0.007 D SO3M wherein D is a polycyclic aromatic radical, said radical being 4 32231; 1 "42968) :22 8'3: selected from the group consisting of the residue of a com- HMO], "43968, 209 0,07 pound containing at least one condensed aromatic nucleus, at 15'.
- R, R R R R,, Z, Z,, L, X, m, r1, d and p are as 7 H070) 100 M0 described in claim 1 and at least one compound having the fol- 1'. 14 97.0 ll-4(968) 112 0.08 75 lowing general formula wherein Y is selected from the group consisting of CH- and N-; wherein R R R,- and R which may be the 10 8 03M soar OgM S 03M (DH-@NHCO r s 03M and said A2 being selected from the group consisting of and wherein when A- is A,, at least one of R R R and R, has a substituent containing an -S0 M group;
- substituted aryloxyl group is selected from the group consisting of phenoxy, tolyloxy, and sulfophenoxy; wherein said group of the alkyl amino series is selected from the group consisting of an alkyl amino, hydroxyalkyl amino and a sulfoalkyl amino group; wherein the group of the arylamino series is selected from the group consisting of an anilino group, a sulfoanilino group, an anisylamino group, a toluidino group, a carboxyanilino group, a hydroxy anilino group, a naphthylamino group and a sulfonaphthylamino group, wherein the heterocyclic nuclear group is selected from the group consisting of a morphonyl and a piperidyl group; wherein the heterocyclic thio group is a benzothiazylthi
- the photographic silver halide emulsion as claimed in 2 claim 13, wherein the weight ratio of said sensitizing dye to the and 0 N N 0 FHN- 0H crr NH-l Yo-fii J i N S O3Na S OaNB V V 5G3 LQ sulfo compound in the emulsion ranges from 1:1 to 1:200.
- the photographic silver halide emulsion as claimed in 16 A photographic light-sensitive element comprising a claim 1, wherein the sensitizing dye is present at a level rangsupport having thereon at least one layer containing the ing from 0.002 to 0.02 grams per gram mol of the silver halide.
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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)
- Plural Heterocyclic Compounds (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP44057545A JPS4925501B1 (enrdf_load_stackoverflow) | 1969-07-21 | 1969-07-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3649288A true US3649288A (en) | 1972-03-14 |
Family
ID=13058724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US56959A Expired - Lifetime US3649288A (en) | 1969-07-21 | 1970-07-21 | Supersensitized silver halide photographic emulsion |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3649288A (enrdf_load_stackoverflow) |
| JP (1) | JPS4925501B1 (enrdf_load_stackoverflow) |
| BE (1) | BE753689A (enrdf_load_stackoverflow) |
| CA (1) | CA975604A (enrdf_load_stackoverflow) |
| DE (1) | DE2036133C3 (enrdf_load_stackoverflow) |
| FR (1) | FR2055343A5 (enrdf_load_stackoverflow) |
| GB (1) | GB1312101A (enrdf_load_stackoverflow) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4002480A (en) * | 1974-03-07 | 1977-01-11 | Fuji Photo Film Co., Ltd. | Photographic silver halide emulsion |
| WO1983000752A1 (en) * | 1981-08-24 | 1983-03-03 | Link, Steven, George | Merocyanine-cyanine-merocyanine (mcm) electrically photosensitive colorants |
| US6022307A (en) * | 1998-07-14 | 2000-02-08 | American Cyanamid Company | Substituted dibenzothiophenes having antiangiogenic activity |
| US6605420B2 (en) * | 2000-08-22 | 2003-08-12 | Fuji Photo Film Co., Ltd. | Photographic processing composition containing bistriazinyl arylenediamine derivative |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54144207A (en) * | 1978-04-30 | 1979-11-10 | Hakko Enpitsu Kk | Method of printing |
| DE10036954C2 (de) * | 2000-07-28 | 2003-12-24 | Agfa Gevaert Ag | Fotografisches Silberhalogenidmaterial |
| JP4452420B2 (ja) * | 2001-04-24 | 2010-04-21 | 富士フイルム株式会社 | 新規化合物 |
| DK1687297T3 (da) * | 2003-11-24 | 2014-09-22 | Prometic Biosciences Inc | Triazindimerer til behandling af autoimmunsygdomme |
| EP1894920A1 (en) * | 2005-06-24 | 2008-03-05 | Japan Science and Technology Agency | Pharmaceutical composition comprising azarhodacyanine compound as active ingredient |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3416927A (en) * | 1964-12-08 | 1968-12-17 | Eastman Kodak Co | Silver halide emulsions containing supersensitizing combinations of merocyanine dyes |
-
1969
- 1969-07-21 JP JP44057545A patent/JPS4925501B1/ja active Pending
-
1970
- 1970-07-20 CA CA088,559A patent/CA975604A/en not_active Expired
- 1970-07-20 FR FR7026635A patent/FR2055343A5/fr not_active Expired
- 1970-07-20 GB GB3514470A patent/GB1312101A/en not_active Expired
- 1970-07-20 BE BE753689D patent/BE753689A/xx unknown
- 1970-07-21 US US56959A patent/US3649288A/en not_active Expired - Lifetime
- 1970-07-21 DE DE2036133A patent/DE2036133C3/de not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3416927A (en) * | 1964-12-08 | 1968-12-17 | Eastman Kodak Co | Silver halide emulsions containing supersensitizing combinations of merocyanine dyes |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4002480A (en) * | 1974-03-07 | 1977-01-11 | Fuji Photo Film Co., Ltd. | Photographic silver halide emulsion |
| WO1983000752A1 (en) * | 1981-08-24 | 1983-03-03 | Link, Steven, George | Merocyanine-cyanine-merocyanine (mcm) electrically photosensitive colorants |
| US6022307A (en) * | 1998-07-14 | 2000-02-08 | American Cyanamid Company | Substituted dibenzothiophenes having antiangiogenic activity |
| US6605420B2 (en) * | 2000-08-22 | 2003-08-12 | Fuji Photo Film Co., Ltd. | Photographic processing composition containing bistriazinyl arylenediamine derivative |
| US6753425B2 (en) | 2000-08-22 | 2004-06-22 | Fuji Photo Film Co., Ltd. | Photographic processing composition containing bistriazinyl arylenediamine derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1312101A (en) | 1973-04-04 |
| JPS4925501B1 (enrdf_load_stackoverflow) | 1974-07-01 |
| DE2036133B2 (de) | 1973-05-30 |
| CA975604A (en) | 1975-10-07 |
| DE2036133C3 (de) | 1973-12-13 |
| DE2036133A1 (de) | 1971-02-11 |
| FR2055343A5 (enrdf_load_stackoverflow) | 1971-05-07 |
| BE753689A (fr) | 1970-12-31 |
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