US3556800A - Photographic silver halide emulsions - Google Patents
Photographic silver halide emulsions Download PDFInfo
- Publication number
- US3556800A US3556800A US747480A US3556800DA US3556800A US 3556800 A US3556800 A US 3556800A US 747480 A US747480 A US 747480A US 3556800D A US3556800D A US 3556800DA US 3556800 A US3556800 A US 3556800A
- Authority
- US
- United States
- Prior art keywords
- group
- dye
- ethyl
- fluoro
- silver halide
- 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 abstract description 62
- 239000000839 emulsion Substances 0.000 title abstract description 39
- 229910052709 silver Inorganic materials 0.000 title abstract description 31
- 239000004332 silver Substances 0.000 title abstract description 31
- 239000000975 dye Substances 0.000 abstract description 79
- 230000001235 sensitizing effect Effects 0.000 abstract description 29
- 150000001450 anions Chemical class 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 81
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- 239000000203 mixture Substances 0.000 description 29
- 239000000298 carbocyanine Substances 0.000 description 24
- 238000002844 melting Methods 0.000 description 23
- 230000008018 melting Effects 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- 229910021607 Silver chloride Inorganic materials 0.000 description 14
- 239000012046 mixed solvent Substances 0.000 description 14
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 229940086542 triethylamine Drugs 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- VIEPPTLGGQIVDC-UHFFFAOYSA-N 8-fluoro-4-methylquinoline Chemical compound C1=CC=C2C(C)=CC=NC2=C1F VIEPPTLGGQIVDC-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 238000003756 stirring Methods 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
- 206010070834 Sensitisation Diseases 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000000243 solution Substances 0.000 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 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- BGTFVZDPIQRVRY-UHFFFAOYSA-N 6-fluoro-4-methylquinoline Chemical compound C1=C(F)C=C2C(C)=CC=NC2=C1 BGTFVZDPIQRVRY-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003248 quinolines Chemical class 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- DDGHBOLOCQWPKE-UHFFFAOYSA-N 1,3-thiazole;hydrobromide Chemical compound [Br-].C1=CSC=[NH+]1 DDGHBOLOCQWPKE-UHFFFAOYSA-N 0.000 description 2
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-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
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- XXTISPYPIAPDGY-UHFFFAOYSA-N n,n-diphenylmethanimidamide Chemical compound C=1C=CC=CC=1N(C=N)C1=CC=CC=C1 XXTISPYPIAPDGY-UHFFFAOYSA-N 0.000 description 2
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical compound [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical group C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical group C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical group C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- WMEPIQQSGOIFIO-UHFFFAOYSA-N 1,3-thiazol-3-ium;hydroxide Chemical compound O.C1=CSC=N1 WMEPIQQSGOIFIO-UHFFFAOYSA-N 0.000 description 1
- ZOZGQVIISSVUNN-UHFFFAOYSA-M 1-ethyl-6-fluoro-4-methylquinolin-1-ium 4-methylbenzenesulfonate Chemical compound C1(=CC=C(C=C1)S(=O)(=O)[O-])C.C(C)[N+]1=CC=C(C2=CC(=CC=C12)F)C ZOZGQVIISSVUNN-UHFFFAOYSA-M 0.000 description 1
- VNOPYGSZUMXSCZ-UHFFFAOYSA-M 1-ethyl-8-fluoro-4-methylquinolin-1-ium 4-methylbenzenesulfonate Chemical compound C1(=CC=C(C=C1)S(=O)(=O)[O-])C.C(C)[N+]1=CC=C(C2=CC=CC(=C12)F)C VNOPYGSZUMXSCZ-UHFFFAOYSA-M 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- YYFMETBLTXDYPO-UHFFFAOYSA-M 3-ethyl-2-methylsulfanyl-1,3-benzothiazol-3-ium ethyl sulfate Chemical compound S(=O)(=O)(OCC)[O-].C(C)[N+]1=C(SC2=C1C=CC=C2)SC YYFMETBLTXDYPO-UHFFFAOYSA-M 0.000 description 1
- MVVFUAACPKXXKJ-UHFFFAOYSA-N 4,5-dihydro-1,3-selenazole Chemical group C1CN=C[Se]1 MVVFUAACPKXXKJ-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-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
- MUDSDYNRBDKLGK-UHFFFAOYSA-N 4-methylquinoline Chemical class C1=CC=C2C(C)=CC=NC2=C1 MUDSDYNRBDKLGK-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MSNAKYOYMNYWLS-UHFFFAOYSA-N C1(=CC=C(C=C1)S(=O)(=O)[O-])C.N(C1=CC=CC=C1)C=CC1=CC=[N+](C2=C(C=CC=C12)F)CC Chemical compound C1(=CC=C(C=C1)S(=O)(=O)[O-])C.N(C1=CC=CC=C1)C=CC1=CC=[N+](C2=C(C=CC=C12)F)CC MSNAKYOYMNYWLS-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WVVMFEDRYOCIKA-UHFFFAOYSA-M [I-].C(C)[N+]1=CC=C(C2=CC=CC(=C12)F)C Chemical compound [I-].C(C)[N+]1=CC=C(C2=CC=CC(=C12)F)C WVVMFEDRYOCIKA-UHFFFAOYSA-M 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical group C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical group C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical group C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- GINSRDSEEGBTJO-UHFFFAOYSA-N thietane 1-oxide Chemical compound O=S1CCC1 GINSRDSEEGBTJO-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
- C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
Definitions
- the present invention relates generally to a photographic silver halide emulsion, and more particularly, to a photographic silver halide emulsion containing a novel cyanine sensitizing dye in which a benzene ring forming the quinoline nucleus has a fluorine atom as a substituent.
- the incorporation of a sensitizing dye in a light-sensitive silver halide emulsion tends to increase the formation of photographic fog in the photographic emulsion layer, especially, when a sensitizing dye having a quinoline nucleus is employed.
- Z represents the non-metallic atoms necessary to complete a heterocyclic ring of the type employed in a cyanine dye
- R and R each represent a member selected Patented Jan. 19 1971 from the group consisting of a lower alkyl group, a substituted alkyl group, an allyl group, a benzyl group, a phenethyl group and a phenoxyethyl group
- X- represents an anion
- 11 may vary from 0 to 1
- n may vary from 0 to l
- in may vary from 1 to 2.
- the novel sensitizing dye of the present invention can spectrally sensitize a silver halide emulsion, and, in particular, it is quite effective in enlarging the spectral lightsensitive region of a gelatino silver halide emulsion.
- An object of this invention is to provide a novel sensitizing dye having a quinoline nucleus.
- Another object of this invention is to provide a lightsensitive silver halide emulsion, containing the novel sensitizing dye mentioned above, will well illustrate reduced fogging.
- the sensitizing dye used in this invention may be prepared by known condensation methods using the compound (Compound II) shown by general Formula II wherein R and X" have the same meaning as heretofore defined.
- R and X contain sulfonic acid or carboxylic acid
- the compound may have a betaine structure by intermolecular ionization, or the compound may be an alkali metal salt.
- Compound II may be prepared by reacting fluoroanilines and methylvinyl ketone using general methods of preparing 4-methylquinolines. The product may then be converted into its quaternary salt.
- a mixture of g. of 6-flu0r0-4-methylquinoline and ethyl-p-toluenesulfonate was heated to 140 C. for 4 hours in an oil bath. After cooling, the product was mixed with ether and acetone, stirred and filtrated to provide g. of the hygroscopic crystal of the sulfonate.
- a mixture of 30 g. of 1-ethyl-6-fiuor0-4-methylquinolinium p-toluenesulfonate and 19.5 g. of diphenyl formamidine was heated to 140 C. for 10 minutes in an oil bath, with intermittent stirring. After cooling, the prod uct was mixed with ether and acetone to cause crystallization, and the precipitate formed was recovered by filtration, washed with acetone and recrystallized from a mixed solvent of methanol and isopropanol to provide 11.5 g. of the sulfonate, having a melting point of 218220 C.
- a mixture of 2.8 g. of 1-ethyl-8-fluoro-4-methylquinolinium p-toluenesulfonate and 2 g. of 3-ethyl-2- methylthiobenzothiazolium ethyl sulfate was dissolved in 60 ml. of ethanol by heating. After adding 4 ml. of triethylamine, the mixture was boiled for 30 minutes under conditions of reflux. After the reaction was finished, an aqueous solution of potassium iodide was added to the system, precipitating the dye.
- the dye thus formed was filtered, washed with ethanol and recrystallized from a mixed solvent of methanol and chloroform to provide 1.9 g. of the dye having a melting point of 258-259 C. (decomposed).
- the maximum absorption maximum of the dye in methanol was 656 my.
- a mixture of 5 g. of 8-fluoro-4-methy1quinoline and 4.6 g. of a-butylonitrile was heated to 140 C., for 6 hours, in an oil bath. After reaction was completed, the product was cooled, mixed with ether and acetone with stirring to cause crystallization. The crystals thus formed were recovered by filtration and recrystallized from a mixed solvent of ethanol and isopropanol to provide 3.6 g. of 1-(3-cyanopropyl) 8 fluoro-4-methylquinolinium bromide, having a melting point of 180-181 C. The product (3.6 g.) was then refluxed for 6 hours with ml.
- the following dyes are within the scope of the present invention and it is believed that the preparation of these dyes will be easily Understand fmm Hm aimm mmtmn..- -..1.
- the novel sensitizing dye used in this invention can spectrally sensitize a silver halide emulsion, and, in particular, is quite elfective for enlarging the spectral lightsensitive region of a gelatino silver halide emulsion.
- the sensitizing dye of this invention will also sufficiently sensitize a photographic emulsion containing hydrophilic colloids other than gelatin, such as agar agar, collodon, water-soluble cellulose derivatives, polyvinyl alcohol and other synthetic or natural hydrophilic resins.
- silver halide emulsion of this invention there may be employed various silver salts, such as, silver chloride, silver bromide, silver iodo-bromide, silver chlorobromide, silver chloroido-bromide, and the like.
- the sensitizing dye of this invention may also be added to a photographic silver halide emulsion which has been preliminarily sensitized by a physical ripening or a chemical ripening.
- one or more sensitizing dyes of this invention may be incorporated in a photographic emulsion by conventional methods.
- the sensitizing dye is incorporated into the photographic emulsion as a solution in a suitable solvent, such as methanol or ethanol.
- a suitable solvent such as methanol or ethanol.
- the amount of the sensitizing dye may be widely varied. For most commercial purposes, a range of 1-150 mg. of dye per one kg. of emulsion, according to the final use, will be acceptable.
- the photographic silver halide emulsion of this invention may be further subjected to super-sensitization and hyper-sensitization, if desired.
- additives that are usually employed in the field, such as, sensitizers, stabilizers, color toning agents, hardening agents, surface active agents, antifoggants, plasticizers, developing accelerators, couplers, and fluorescent whitening agents may be incorporated into the photographic silver halide emulsion.
- the silver halide emulsion of this invention also contains at least one of the following materials: Compound A-I, Compound A-II, Compound A- III or Compound B, described in Japanese patent publication No. 4,724/53, Japanese patent application No. 11,- 669/ 67, Japanese patent application No. 52,488/65, and Japanese patent publication No. 81,697/ 65, respectively, the sensitivity of the spectral sensitizing regions can be increased. That is, a super-sensitizing effect can be obtained, and further, the spectral sensitivity decrease during preservation of light sensitive elements having the light-sensitive layers of the silver halide emulsions of this invention can be halted to a great extent.
- Compound A-I is represented by the general formula:
- R and R each may represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an acyl group, an alkoxyl group, an unsubstituted or substituted carbamyl group, a hetercyclic ring; and X and X each represent a hydrogen atom or SO I-I.
- Compound A-II is represented by the following general formula:
- R and R each represents a halogen atom, a hydroxyl group, or NHR (where R represents an aryl group or an aralkyl group); D represents a hydogen atom, an alkali metal, an ammonium group or an amine salt.
- Compound B is a condensation product of formaldehyde and a compound represented by the following formula:
- the sensitizing dyes of this invention were incorporated in a silver chlor-bromide emulsion (AgBr 40 moles; AgCl 60 moles).
- the photographic emulsion thus prepared was applied to a cellulose triacetate film and dried to provide a light-sensitive film.
- the light sensitive emulsion layer was exposed to the light of a tungsten lamp, using a diffraction grating spectrograph, developed. The spectral sensitivity characteristics were then measured.
- a developer having the composition shown below (Table 1) was used:
- Table 3 shows the results of a comparison of the fog densities when employing the silver halide emulsions of this invention and when employing identical silver halide emulsions containing the conventional sensitizing dyes shown below (not the novel dyes of the present invention).
- sensitizing dye is selected from the group consisting of 8-fluoro-4-methylquinoline; 6-fluoro-4-methylquinoline; 1-ethyl-8-fluoro-4-methylquinolinium iodide; 1-ethyl-6-fluoro-4-methyl-quinolinium iodide; 1-ethyl-8-fiuoro-4-methylquinolinium p-toluenesulfonate; 1-ethyl-6-fluoro-4-methylquinolinium p-toluenesulfonate; 4- Z-acetanilidovinyl) l -ethyl-8-fluoro-quinolinium p-toluenesulfonate; 4-(Z-anilinovinyl)-1-ethyl-6-fluoro-quinolinium n-toluenesnlfnmrp- 13 1,1'-diethy1-8
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4772165 | 1965-07-25 | ||
| JP4772167A JPS521299B1 (enrdf_load_stackoverflow) | 1967-07-25 | 1967-07-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3556800A true US3556800A (en) | 1971-01-19 |
Family
ID=26387880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US747480A Expired - Lifetime US3556800A (en) | 1965-07-25 | 1968-07-25 | Photographic silver halide emulsions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3556800A (enrdf_load_stackoverflow) |
| BE (1) | BE718499A (enrdf_load_stackoverflow) |
| FR (1) | FR1588846A (enrdf_load_stackoverflow) |
| GB (1) | GB1210009A (enrdf_load_stackoverflow) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4677053A (en) * | 1983-04-15 | 1987-06-30 | Yuji Mihara | Silver halide photographic materials |
| EP1750173A1 (en) | 2005-08-04 | 2007-02-07 | Fuji Photo Film Co., Ltd. | Silver halide photosensitive material and packaged body containing the same |
| CN102702769A (zh) * | 2012-06-20 | 2012-10-03 | 大连理工大学 | 一类绿光荧光菁染料、制备方法及其应用 |
| US20230107256A1 (en) * | 2017-03-30 | 2023-04-06 | The Board Of Regents Of The University Of Texas System | Quinoline derived small molecule inhibitors of nicotinamide n-methyltransferase (nnmt) and uses thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495692B1 (en) | 1996-12-10 | 2002-12-17 | Abbott Laboratories | Helium-neon excitable reticulocyte dyes derivable from halolepidines |
-
1968
- 1968-07-23 FR FR1588846D patent/FR1588846A/fr not_active Expired
- 1968-07-24 BE BE718499D patent/BE718499A/xx not_active IP Right Cessation
- 1968-07-25 GB GB35662/68A patent/GB1210009A/en not_active Expired
- 1968-07-25 US US747480A patent/US3556800A/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4677053A (en) * | 1983-04-15 | 1987-06-30 | Yuji Mihara | Silver halide photographic materials |
| EP1750173A1 (en) | 2005-08-04 | 2007-02-07 | Fuji Photo Film Co., Ltd. | Silver halide photosensitive material and packaged body containing the same |
| CN102702769A (zh) * | 2012-06-20 | 2012-10-03 | 大连理工大学 | 一类绿光荧光菁染料、制备方法及其应用 |
| US20230107256A1 (en) * | 2017-03-30 | 2023-04-06 | The Board Of Regents Of The University Of Texas System | Quinoline derived small molecule inhibitors of nicotinamide n-methyltransferase (nnmt) and uses thereof |
| US12071409B2 (en) * | 2017-03-30 | 2024-08-27 | The Board Of Regents Of The University Of Texas | Quinoline derived small molecule inhibitors of nicotinamide N-methyltransferase (NNMT) and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1210009A (en) | 1970-10-28 |
| BE718499A (enrdf_load_stackoverflow) | 1968-12-31 |
| DE1772913B1 (de) | 1972-01-13 |
| FR1588846A (enrdf_load_stackoverflow) | 1970-03-16 |
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