US3813249A - Light sensitive photographic material - Google Patents
Light sensitive photographic material Download PDFInfo
- Publication number
- US3813249A US3813249A US00222663A US22266372A US3813249A US 3813249 A US3813249 A US 3813249A US 00222663 A US00222663 A US 00222663A US 22266372 A US22266372 A US 22266372A US 3813249 A US3813249 A US 3813249A
- Authority
- US
- United States
- Prior art keywords
- emulsion
- layer
- photographic material
- silver halide
- formula
- 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
- 239000000463 material Substances 0.000 title abstract description 74
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical class [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 135
- 239000010410 layer Substances 0.000 description 96
- -1 silver halide Chemical class 0.000 description 64
- 229910052709 silver Inorganic materials 0.000 description 61
- 239000004332 silver Substances 0.000 description 61
- 150000001875 compounds Chemical class 0.000 description 40
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 34
- 239000006185 dispersion Substances 0.000 description 21
- 108010010803 Gelatin Proteins 0.000 description 20
- 239000008273 gelatin Substances 0.000 description 20
- 229920000159 gelatin Polymers 0.000 description 20
- 235000019322 gelatine Nutrition 0.000 description 20
- 235000011852 gelatine desserts Nutrition 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 238000011109 contamination Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 239000000428 dust Substances 0.000 description 7
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- PTPLXVHPKMTVIW-FPLPWBNLSA-N (Z)-hydroxyimino-oxido-phenylazanium Chemical compound O\N=[N+](/[O-])c1ccccc1 PTPLXVHPKMTVIW-FPLPWBNLSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 3
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 2
- 229940093471 ethyl oleate Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- LJCWONGJFPCTTL-UHFFFAOYSA-N 4-hydroxyphenylglycine Chemical compound OC(=O)C(N)C1=CC=C(O)C=C1 LJCWONGJFPCTTL-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
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940116335 lauramide Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- MFARGUPPFBTESX-UHFFFAOYSA-N n,n-dibutyldodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCCC)CCCC MFARGUPPFBTESX-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 125000002264 triphosphate group Chemical class [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood 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
- G03C1/33—Spot-preventing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/136—Coating process making radiation sensitive element
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/139—Defect coating
Definitions
- This invention relates to a light sensitive photographic material.
- Atmospheric dust has a very complex constitution but most atmospheric dust, especially that in the atmosphere of industrial areas, contains fine particles of metal, metal oxides and metal salts.
- Film base casting machines and film base coating machines comprise a large number of metal parts, for example copper or steel rollers, so that metal dust particles are continously produced by the working of such machines and these dust particles often settle on the film base or on the emulsion layer on the film base. Further, traces of metals or their compounds are often present in gelatin and other materials from which the various layers of the photographic material are made.
- British Patent Specification No. 623,488 describes the use of aldoximes which are added to the developer or the emulsion in order to decrease the activity of cupric ions which catalyse aerial fogging.
- US. Pat. No. 2,239,284 describes the use of alkali metaphosphates, alkali hexametaphosphates, alkali triphosphates and alkali pyrophosphates for iron, copper and aluminium ions.
- latent image regression is the defect known as latent image regression. This manifests itself as an apparent decrease in the sensitivity of the photographic material. Usually the longer the period over which exposed material is kept before development the greater the apparent decrease in the sensitivity of the material. This apparent decrease in sensitivity is enhanced by storing the material at elevated temperatures. The exact cause of latent image regression is not at present known with any certainty but it is thought to be due in some instances at least to the presence in the emulsion of iron or copper.
- a photographic material which comprises a support base having coated thereon one or more layers, at least one of which is a photosensitive layer, there being present in at least one layer of the material a water-soluble N-nitroso oxime of the formula:
- A represents a phenyl or naphth-lor -2-yl radical or a phenyl or naphth-lor -2-yl radical substituted by one or two members selected from halogen, hydrogen, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms, aralkyl and hydroxy and R is a cation.
- a cation R for example hydrogen, ammonium, lithium, sodium or potassium may be mentioned.
- N-nitroso oximes are known compounds and have found use in various industries and analytical techniques as metal chelating agents.
- N (III) If- 0 NH
- N 0 0131:
- N O I
- N-nitroso-oxime compound of formula I may be present in any layer of the photographic material, for example a photosensitive layer, in any inter layer of the material, in a subbing layer, in a supercoat layer or in a layer distal to the photosensitive layer, for example in an anti-halation layer.
- the photographic material comprises a silver halide emulsion layer and the compound of formula I is present in this emulsion layer or in a layer in operative contact with this layer
- the presence of the compound of formula I reduces the tendency of any metallic contamination of the photographic material to produce spots in any of the layers of the material, reduces the tendency of any metallic contamination to react with the silver halide emulsion layer and produce desensitized or sensitized spot marks and reduces the tendency of the photographic material to exhibit latent image instability.
- the photographic material does not comprise a silver halide emulsion layer or the compound of formula I is not in the silver halide emulsion layer nor in a layer in operative contact therewith, then the presence of the compound of formula I in the photographic material acts only to reduce the tendency of any metallic contamination of the photographic material to produce spots in the layer in which it is present or in any layer in operative contact therewith.
- photographic material which comprises a support base carrying a silver halide emulsion layer, there being present in the silver halide emulsion layer or in a layer in operative contact therewith a compound of formula I.
- layer in operative contact with a silver halide emulsion layer is meant a layer in contact with the emulsion layer so that during coating of the layers some at least of the water-soluble N-nitroso-oxime of formula I is able to migrate from the layer in which it is coated into the emulsion layer.
- the N-nitroso-oxime compound of formula I is added to the silver halide emulsion layer in an amount between 0.01 to 10 g. per mole of silver halide in the emulsion.
- the compound is added as an aqueous or alcoholic solution to the emulsion just prior to coating of the emulsion.
- the preferred amount of the nitroso-oxime compound of formula I to be present in the material depends on the amount of metallic contamination present. Thus if coatings on a specific coating machine exhibit particularly high metallic contamination then more of the nitrosooxime compound will be required in photographic materials coated thereon than in material coated on machines wherein the coatings made thereon are not so severely contaminated with metallic particles.
- N-nitroso-oxime compounds of formula I when present in photographic material do not occasion any deleterious eifects in the photographic material. In particular they do not cause fogging of the emulsion. Moreover, of course, they do not cause serious deterioration of the latent image. Further they do not cause any deterioration in the mechanical properties of the emulsion.
- N-nitroso-oxime compounds of formula I act more efiiciently in preventing latent image instability and spot marks when there is present in the layer of the photographic material which contains the N-nitroso-oxime compound, or in a layer in operative contact therewith, a dispersion of a water-insoluble organic solvent-soluble high-boiling point liquid, a so-called oil former.
- oil-former employed should be chemically and photographically inert towards the layer of the photographic material in which it is incorporated and towards photographic processing baths.
- oil-formers having boiling points above 150 C. are preferred.
- the oil-former should have a refractive index close to that of the binder, usually gelatin, of the layer in which it is dispersed.
- oil-formers which can be used are octadecanol, high boiling petroleum fractions, dibutyl phthalate, 1,2-dimethoxybenzene, diphenyl, diphenylether, NzN-dibutyl-lauramide, 2,4 di-n-amylphenyl, tricresyl phosphate, benzophenone, and ethyl oleate; some of these oil-formers and others suitable for the purpose are set out in British Patent Specification Nos. 541,589, 633,812 and 820,329.
- a solvent dispersion for example in gelatin, may be dried and reconstituted in water as required.
- the oil-former may also be dissolved in a watermisible solvent such as acetone, methanol or methyl acetate, a dispersing agent added and the whole added to an aqueous gelatin solution or gelatin silver halide emulsion when a fine dispersion of the oil-former is obtained.
- Dispersing agents which may be used to aid and stabilise the dispersions include the sodium salt of dioctyl and sulphosuccinate, sodium lauryl sulphate and triisopropylnaphthalene sulphonate.
- the dispersion may be elfected with the aid of a ho mogenizer, colloid mill or the like.
- the preferred oil-former for use in the present invention is dibutyl phthalate. 7
- N-nitroso-oximes and metal contaminants has some effect on latent image stability and in the production of spot marks, but a much reduced effect compared with the metal contaminants per se, so that when this complex is completely removed from the silver halide phase an even greater improvement in latent image stability and reduction in spot marks is obtained.
- Complexes formed between the N-nitroso-oximes of formula I and copper or iron are more soluble in the oil-formers than in the gelatin or other binder phase of the emulsion and thus the complex is preferentially extracted from the silver halide phase into the oil-former phase of the layers.
- photographic material which comprises a support base having coated thereon one or more layers, at least one of which is a photographic layer, there being present in at least one layer of the material a dispersion of an oil-former and there being present in the same layer or in a layer in operative contact therewith a N-nitroso-oxime of formula I.
- photographic material which comprises a support base carrying thereon a silver halide emulsion layer having dispersed therein a water-insoluble organic-solvent-soluble high boiling point oil-former, there being present in the silver halide emulsion layer or in a layer in operative contact therewith a N-nitrosooxime compound of formula I.
- the N-nitrosooxime is present in the silver halide emulsion layer
- the preferred oil-former is dibutyl phthalate
- the preferred N-nitroso-oxime is the compound of formula II.
- N-nitroso-oxime compounds of formula I act more eiiiciently in preventing spot marks due to copper contamination when there is present in the layer of the photographic material which contains the N- nitroso-oxime compound, or in a layer in operative contact therewith, salicylaldoxime. Some increased effect is apparent also in the prevention of spots due to iron contamination.
- photographic material which comprises a support base having coated thereon one or more layers, at least one of which is a photographic layer, there being present in at least one layer of the material salicylaldoxime and there being present in the same layer or in a layer in operative contact therewith a N-nitroso-oxime of formula I.
- the amount of salicylaldoxime present in the silver halide emulsion is from 0.01-10 g. per mole of silver halide in the emulsion.
- N-nitroso-oxime compounds of formula I may be added to photographic emulsions at any stage in the emulsion making process provided they remain present in the finished emulsion.
- the silver halide emulsion to which the N-nitrosooxime compounds of formula I may be added may comprise any of the normal silver halides, for example, silver chloride, silver bromide or silver iodobromide.
- the emulsion binder is preferably gelatin but may comprise other polymeric substances for example polyvinyl alcohol, polyvinyl pyrrolidone, ethyl cellulose or an alginate, either alone or in admixture with the gelatin.
- EXAMPLE 1 A slow fine grain iodobromide emulsion was prepared, in gelatin solution, having 3.2 mole percent of silver iodide, the pH of the emulsion being adjusted to 6.0 and the pAg of the emulsion being adjusted to 8.4. This emulsion was digested at an elevated temperature in the presence of sodium thiosulphate and a gold salt to maximum sensitivity. The emulsion was then stabilized by the addition of a tetraazaindene compound and cooled. A wetting agent was then added to the emulsion, which was reheated and coated onto film strips. This was the control emulsion A.
- the gelatin dispersion of dibutyl phthalate was made by adding 5% of dibutyl phthalate to 129 g. of gelatin dissolved to form a concentrated aqueous solution, ml. of Perminal BX, a naphthalene sulphonate based dispersing agent marketed by Imperial Chemical Industries Limited, was then added to the mixture and the mixture was mechanically stirred in order to disperse the dibutyl phthalate in the gelatin solution.
- EXAMPLE 2 Three samples A, B and C of a fast coarse-grained iodobromide emulsion were prepared as in Example 1. Samples of these emulsions were exposed, incubated and processed as in Example 1.
- test 1 the speed loss of the emulsion at 0.1 above fog was determined.
- test 2 the speed loss or gain at 1.5 above fog was determined.
- test 3 the development time of the emulsions was lowered to 3 minutes and the speed loss or gain at 0.1 above fog was determined.
- test 4 the development time of the emulsions was also 3 minutes and the speed loss or gain at 1.5 above fog was determined.
- Emulsion 1 2 3 4 EXAMPLE 3 A slow fine grain iodobromide emulsion was prepared and coated exactly as in Example 1. This was the control emulsion A.
- EXAMPLE 4 A slow fine grain iodobromide emulsion was prepared and coated as in Example 1. This was the control emulsion A.
- emulsion F and G Similar emulsions F and G were prepared and coated except that in the case of emulsion F 160 mols of 1% aqueous solution of the compound of formula IV was added per mole of silver halide.
- emulsion G 7 g. of a dibutyl phthalate dispersion (prepared as in Example 1) was added to the emulsion after digestion and then 160 mols of a 1% aqueous solution of the compound of formula IV was added per mole of silver halide.
- sample was prepared (referred to as N) except that there was added to 1 kg. of the silver halide emulsion just prior to coating 100 ml. of a 1% ethanolic solution of the compound of formula H.
- a third sample P was prepared; in this sample there was added to the silver halide emulsion prior to coating, in addition to the compound of formula II, 100 ml. of a gelatin dispersion containing 30% dibutyl phthalate.
- a fourth sample Q was prepared as M except that there was added to 1 kg. of the silver halide emulsion just prior to coating 100 ml. of a 1% ethanolic solution of the compound of formula III.
- a fifth sample R was prepared and in this sample there was added to 1 kg. of the silver halide emulsion prior to coating in addition to the compound of formula HI, 100 ml. of a gelatin dispersion containing 30% dibutyl phthalate.
- a sixth sample S was prepared as sample M except that there was added to 1 kg. of the silver halide emulsion just prior to coating 100 ml. of a 1% ethanolic solution of the compound of formula VII.
- a seventh sample T was also prepared and in this sample there was added to 1 kg. of the silver halide emulsion just prior to coating 100 ml. of a gelatin dispersion containing 30% dibutyl phthalate in addition to the compound of formula VII.
- Samples M, N, -P, Q, R, S and T were exposed to light and developed for 4 minutes in a Phenidone/hydroquinone based developer. On inspection, after drying, sample M was found to have numerous light patches centered on the copper particles. Samples N, Q and S were found to have some light patches centered on the copper particles, but
- EXAMPLE 6 This example illustrates the effect caused by iron and rust on the silver halide emulsion and illustrates the improvement obtained by the additives used in the present invention.
- a silver iodobromide emulsion having a pH of 6.5 was applied to a gelatin layer which contained very fine iron powder and rust coated on a film support (sample VIII).
- a similar sample Y was prepared except that there was added to 1 kg. of the silver iodobromide emulsion just prior to coating 75 mols of a 1% aqueous solution of the compound of formula IH.
- Similar samples U, V, W and Z were prepared containing respectively 75 mols of a 1% solution of the compound of formulae III, IV, V and VIII.
- Samples X, Y, Z, U, V and NV were then light exposed and developed for 4 minutes in a l-phenyl-3- pyrazolidone/hydroquinone based developer.
- sample VIII there were found to be a large number of sensitized black spots which were due to (metal ions from) the iron and rust coming into contact with the silver halide emulsion and causing sensitized marks.
- samples Y, Z, U, V and W the number of sensitized black marks was considerably reduced compared with sample VHI.
- EXAMPLE 7 A silver iodobromide emulsion having a pH of 6.5 was applied to a gelatin layer which contained very fine copper particles coated onto a film support (sample A). Similar samples were prepared except that there were added to the silver iodobromide emulsion 6 mols of a 20% ethanolic solution of salicylaldoxime per mole of silver halide (sample B) mols of a 2% aqueous solution of the ammonium salt of N-nitrosoN-phenylhydroxylamine (the compound of formula II) per mole of silver halide (sample C) and finally salicylaldoxime and the ammonium salt of N-nitroso-N-phenylhydroxylamine ta gether in the above quantities (sample D).
- Samples A, B, C and D were then light exposed and developed for 4 minutes in a 1-phenyl-3-pyrazolidone/hydroquinonebased developer.
- sample A there were numerous desensitized (white) spots centered on the copper particles.
- sample B these desensitized spots were slightly reduced in size, while in sample C both their numbers and their intensities were greatly reduced.
- sample D no desensitized areas were observed.
- a photographic material which comprises a support base having coated thereon one or more layers, at least one of which is a photosensitive silver halide emulsion layer, there being present in at least one layer of the material a water-soluble N-nitroso-oxime of the formula wherein A represents a phenyl or naphth-lor -2-yl radical or a phenyl or naphth-lor -2-yl radical substituted by one or two members selected from hydrogen, halogen, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms and aralkyl and R is a cation.
- a photographic material according to claim 1 which comprises a compound of formula I defined in claim 1 wherein A is a phenyl-, naphth-l-yl-, 2,3- or 3,4-dimethylphen-1-yl-, 2- or 4-methyl-pheny-l-yl-, 4-chlorophen-l-yl-, Z-chloro-S-methyl-phen-l-yl-, 2- or 4-ethylpheny-l-ylor 4-(fl-hydroxyethyl)-phen-l-yl-radical and R is the NH.; group as the water-soluble N-nitroso-oxime.
- a photographic material according to claim 1 which comprises a compound of formula I defined in claim 1 wherein A is phenyl and R is the NH., group as the water-soluble N-nitroso-oxime.
- a photographic material according to claim 1 which comprises a compound of formula I defined in claim 1 wherein A is naphth-l-yl and R is the NH.; group as the water-soluble N-nitroso-oxime.
- a photographic material according to claim 1 which comprises at least one layer containing dispersed therein a water-insoluble organic-solvent-soluble high 'boiling point oil-former, selected from the group consisting of a high boiling petroleum fraction, dibutyl phthalate, 1,2- di-methoxybenzene, verotrole, diphenyl, diphenylether, N,N-dibutyllauramide, 2,4 di-n-amylphenyl, tricresylphosphate, benzophenone and ethyloleate and a watersoluble N-nitroso-oxime of the formula I A-N-O-R N L .0
- a and R have the meanings given in claim 1 which oxime is contained in the same layer or in a layer adjacent to the layer containing the oil-former.
- a photographic material according to claim 5 which comprises a compound of the formula I defined in claim 5 wherein A is phenyl and R is the -NH.; group as the water-soluble N-nitroso-oxime.
- a photographic material according to claim 5 which comprises a compound of the formula I defined in claim 5 wherein A is naphth-l-yl and R is the -NH.; group as the water-soluble N-nitroso-oxime.
- a photographic material according to claim 1 which comprises a silver halide emulsion layer as the photosensitive layer and a water-soluble N-nitroso-oxime of formula I wherein A and R have the meanings given in claim 1 which oxime is contained in said silver halide emulsion layer or in a layer adjacent to said layer.
- a photographic material according to claim 9 which comprises a compound of formula I defined in claim 9 wherein A is phenyl and R is the ---NH.; group.
- a photographic material according to claim 9 which comprises a compound of formula I defined in claim 9 wherein A is naphth-l-yl and R is the NH; group.
- a photographic material according to claim 15 which comprises a compound of formula I wherein A is phenyl and R is the -NH group as water-soluble N- nitroso-oxime.
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Abstract
A PHOTOGRAPHIC MATERIAL COMPRISING IN AT LEAST ONE LAYER A WATER-SOLUBLE N-NITROSO-OXIME OF THE FORMULA
O=N-N(-A)-O-R
WHEREIN A REPRESENTS A PHENYL OR NAPHTH-1- OR -2-YL RADICAL OR A PHENYL OR NAPHTH-1- OR -2-YL RADICAL SUBSTITUTED BY ONE OR TWO MEMBERS SELECTED FROM HYDROGEN, ALKYL HAVING 1 TO 5 CARBON ATOMS, ALKOXY HAVING 1 TO 5 CARBON ATOMS, HYDROXYALKYL HAVING 1 TO 5 CARBON ATOMS, ARALKYL AND HYDROXY AND R IS A CATION AS MEANS FOR REDUCING SPOT FORMATION IS DESCRIBED.
O=N-N(-A)-O-R
WHEREIN A REPRESENTS A PHENYL OR NAPHTH-1- OR -2-YL RADICAL OR A PHENYL OR NAPHTH-1- OR -2-YL RADICAL SUBSTITUTED BY ONE OR TWO MEMBERS SELECTED FROM HYDROGEN, ALKYL HAVING 1 TO 5 CARBON ATOMS, ALKOXY HAVING 1 TO 5 CARBON ATOMS, HYDROXYALKYL HAVING 1 TO 5 CARBON ATOMS, ARALKYL AND HYDROXY AND R IS A CATION AS MEANS FOR REDUCING SPOT FORMATION IS DESCRIBED.
Description
United States Patent 3,813,249 LIGHT SENSITIVE PHOTOGRAPHIC MATERIAL Aaron David Ezekiel, Elvin Frederick William Thurston, Michael Frederick Harper, and Malcom Barlow Wood, Ilford, England, assignors to Ilford Limited, Ilford, England No Drawing. Filed Feb. 1, 1972, Ser. No. 222,663 Claims priority, application Great Britain, Feb. 4, 1971, 3,957/71 Int. Cl. G03c 1/02, 1 76 U.S. Cl. 96-67 16 Claims ABSTRACT OF THE DISCLOSURE A photographic material comprising in at least one layer a Water-soluble N-nitroso-oxime of the formula A-NOR N=O (I) wherein A represents a phenyl or naphth-lor -2-yl radical or a phenyl or naphth-lor -2-yl radical substituted by one or two members selected from hydrogen, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms, aralkyl and hydroxy and R is a cation as means for reducing spot formation is described.
This invention relates to a light sensitive photographic material.
Normally photographic materials are manufactured under conditions wherein as little dust as possible is present in the atmosphere. However, despite every precaution it is not possible completely to prevent dust particles from being deposited on the photographic material in the course of its manufacture. Atmospheric dust has a very complex constitution but most atmospheric dust, especially that in the atmosphere of industrial areas, contains fine particles of metal, metal oxides and metal salts. Film base casting machines and film base coating machines comprise a large number of metal parts, for example copper or steel rollers, so that metal dust particles are continously produced by the working of such machines and these dust particles often settle on the film base or on the emulsion layer on the film base. Further, traces of metals or their compounds are often present in gelatin and other materials from which the various layers of the photographic material are made.
When photographic material containing metal particles and in particular particles of aluminium, chromium, iron, nickel and copper and the oxides and salts of these metals, is exposed and processed, these particles appear as spots visible to the naked eye. These spots are often many times bigger than the dust particles itself and are the results of the metal or its salts or oxidation products either desensitizing the photographic silver halide emulsion surrounding it or, in other cases, sensitizing the emulsion surrounding it. Furthermore, gross contamination by metal particles can result in spots being formed in non-emulsion layers of the photographic material which contain such particles.
Several types of additives have been proposed for the prevention of such spots. For example, British Patent Specification No. 623,488 describes the use of aldoximes which are added to the developer or the emulsion in order to decrease the activity of cupric ions which catalyse aerial fogging. US. Pat. No. 2,239,284 describes the use of alkali metaphosphates, alkali hexametaphosphates, alkali triphosphates and alkali pyrophosphates for iron, copper and aluminium ions. British Patent Specification No. 524,087 mentions the use of p-hydroxy phenylglycine in a gelatinosilver halide emulsion layer, and in British Patent Speci' fication No. 691,715 the use of ethylene diamine-tetraacetic acid in silver halide emulsions for inhibiting spots is described.
ice
However, it has been found that these compounds have limited effects in certain emulsions and their presence in emulsions often causes deleterious side effects such as deterioration of the latent image, fogging of the emulsion during storage, or deterioration in the mechanical properties of the photographic material, e.g. greater susceptibility to scratching.
Further, it is important in silver halide photographic materials that the latent image formed on exposure should be relatively stable over the period from exposure to development. The most common and serious form of latent image instability is the defect known as latent image regression. This manifests itself as an apparent decrease in the sensitivity of the photographic material. Usually the longer the period over which exposed material is kept before development the greater the apparent decrease in the sensitivity of the material. This apparent decrease in sensitivity is enhanced by storing the material at elevated temperatures. The exact cause of latent image regression is not at present known with any certainty but it is thought to be due in some instances at least to the presence in the emulsion of iron or copper. It is thought that these substances, when present in the exposed silver halide emulsion, oxidize some of the partially reduced silver which constitutes the latent image. In the case of color photographic material containing several silver halide emulsion layers the consequences of latent image regression are more serious because they are more obvious since it generally arises that the regression is not uniform for the several emulsion layers and there is consequently a shift in the color balance as well as an apparent loss of sensitivity. Generally latent image progression, another form of latent image instability, is not such a serious defect but when it occurs in color photographic material in one emulsion layer but not in another it can cause a shift in the color balance of the final color image.
It is the object of the present invention to provide a photographic material having additives therein which act to reduce the tendency of the photographic material to exhibit spot formation due to metal particle, metal oxide and metal salt contamination. Further it is the object of the present invention to provide silver halide emulsion photographic material which comprises an additive in operative contact with the silver halide emulsion serving to reduce the tendency of the emulsion to exhibit latent image instability. Further it is the object of the present invention to provide additives for photographic materials for the foregoing purposes which have a reduced tendency to produce undesirable side effects in the photographic material which contain them.
According to the present invention there is provided a photographic material which comprises a support base having coated thereon one or more layers, at least one of which is a photosensitive layer, there being present in at least one layer of the material a water-soluble N-nitroso oxime of the formula:
wherein A represents a phenyl or naphth-lor -2-yl radical or a phenyl or naphth-lor -2-yl radical substituted by one or two members selected from halogen, hydrogen, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms, aralkyl and hydroxy and R is a cation.
As a cation R, for example hydrogen, ammonium, lithium, sodium or potassium may be mentioned.
The N-nitroso oximes are known compounds and have found use in various industries and analytical techniques as metal chelating agents.
Preferred compounds for use in the present invention are those of formula (I) wherein A is a phenyl-, naphth- 1-yl-, 2,3- or 3,4-dimethyl-phen-l-yl-, 2- or 4 methylpheny-1-yl-, 4-chloro-phen-1-yl-, 2-chloro-5-methyl-phen- 1-yl-, 2- or 4-ethylphenyl-1-ylor 4 3 hydroxyethyl)- phen-l-yl-radical and R is the -NH.; group and which correspond to the formulae If-O-NHI N=O I III- NH| N= (III) If- 0 NH| 0 HI @0 H: If- 0 NH4 III- 0 NH| N=0 0131:
III-0 NH| N= (VII) III-O NH4 =0 (VIII) III-O NH| N=O I|-ION H4 N:
N-O-NHa 1 1:0 (XII) Compound II and compound III are the preferred ones.
Compounds IV to XII have been synthesized by condensing the respective hydroxylamine with n-butylnitrite in the presence of ammonia. The structures of these compounds IV to XII has been established unequivocally from the evidence obtained from elementary analysis, infrared and proton magnetic resonance spectrocopy.
It is to be understood that the N-nitroso-oxime compound of formula I, may be present in any layer of the photographic material, for example a photosensitive layer, in any inter layer of the material, in a subbing layer, in a supercoat layer or in a layer distal to the photosensitive layer, for example in an anti-halation layer. When the photographic material comprises a silver halide emulsion layer and the compound of formula I is present in this emulsion layer or in a layer in operative contact with this layer, the presence of the compound of formula I reduces the tendency of any metallic contamination of the photographic material to produce spots in any of the layers of the material, reduces the tendency of any metallic contamination to react with the silver halide emulsion layer and produce desensitized or sensitized spot marks and reduces the tendency of the photographic material to exhibit latent image instability.
When the photographic material does not comprise a silver halide emulsion layer or the compound of formula I is not in the silver halide emulsion layer nor in a layer in operative contact therewith, then the presence of the compound of formula I in the photographic material acts only to reduce the tendency of any metallic contamination of the photographic material to produce spots in the layer in which it is present or in any layer in operative contact therewith.
Therefore, according to a preferred embodiment of the invention, there is provided photographic material which comprises a support base carrying a silver halide emulsion layer, there being present in the silver halide emulsion layer or in a layer in operative contact therewith a compound of formula I.
By layer in operative contact with a silver halide emulsion layer is meant a layer in contact with the emulsion layer so that during coating of the layers some at least of the water-soluble N-nitroso-oxime of formula I is able to migrate from the layer in which it is coated into the emulsion layer.
Preferably when the photographic material contains a silver halide emulsion the N-nitroso-oxime compound of formula I is added to the silver halide emulsion layer in an amount between 0.01 to 10 g. per mole of silver halide in the emulsion. Preferably the compound is added as an aqueous or alcoholic solution to the emulsion just prior to coating of the emulsion. It is to be understood that the preferred amount of the nitroso-oxime compound of formula I to be present in the material depends on the amount of metallic contamination present. Thus if coatings on a specific coating machine exhibit particularly high metallic contamination then more of the nitrosooxime compound will be required in photographic materials coated thereon than in material coated on machines wherein the coatings made thereon are not so severely contaminated with metallic particles.
It has been found that the N-nitroso-oxime compounds of formula I when present in photographic material do not occasion any deleterious eifects in the photographic material. In particular they do not cause fogging of the emulsion. Moreover, of course, they do not cause serious deterioration of the latent image. Further they do not cause any deterioration in the mechanical properties of the emulsion.
It has been found that the N-nitroso-oxime compounds of formula I act more efiiciently in preventing latent image instability and spot marks when there is present in the layer of the photographic material which contains the N-nitroso-oxime compound, or in a layer in operative contact therewith, a dispersion of a water-insoluble organic solvent-soluble high-boiling point liquid, a so-called oil former.
Preferably the oil-former employed should be chemically and photographically inert towards the layer of the photographic material in which it is incorporated and towards photographic processing baths. In general, oil-formers having boiling points above 150 C. are preferred.
It is, further, most advantageous that the oil-former should have a refractive index close to that of the binder, usually gelatin, of the layer in which it is dispersed.
Examples of suitable oil-formers which can be used are octadecanol, high boiling petroleum fractions, dibutyl phthalate, 1,2-dimethoxybenzene, diphenyl, diphenylether, NzN-dibutyl-lauramide, 2,4 di-n-amylphenyl, tricresyl phosphate, benzophenone, and ethyl oleate; some of these oil-formers and others suitable for the purpose are set out in British Patent Specification Nos. 541,589, 633,812 and 820,329.
An emulsion layer containing a dispersion of the oilformer may be obtained in a variety of ways. The oilformer may be dispersed in water or gelatin solution or in any aqueous solution of a water-soluble binder which ismiscible with and compatible with the layer e.g. the silver halide emulsion layer, and the dispersion so obtained added to the layer. Alternatively, the oil-former may be dissolved in a low boiling or water-miscible solvent prior to being dispersed. If a low-boiling solvent has been used this is removed by evaporation. If a watermiscible solvent has been used in a gelatin layer this solvent may be removed by washing the gelled and shredded dispersion. If desired a solvent dispersion, for example in gelatin, may be dried and reconstituted in water as required. The oil-former may also be dissolved in a watermisible solvent such as acetone, methanol or methyl acetate, a dispersing agent added and the whole added to an aqueous gelatin solution or gelatin silver halide emulsion when a fine dispersion of the oil-former is obtained.
Dispersing agents which may be used to aid and stabilise the dispersions include the sodium salt of dioctyl and sulphosuccinate, sodium lauryl sulphate and triisopropylnaphthalene sulphonate.
The dispersion may be elfected with the aid of a ho mogenizer, colloid mill or the like.
:A proportion of 0.5 to 5% by weight of a said oilformer layer, based on the formulated silver halide emulsion has been found to be suitable.
The preferred oil-former for use in the present invention is dibutyl phthalate. 7
It is not known with certainty why the presence of a dispersion of an oil-former in the layer containing the nitroso-oxime compound, or in a layer in operative contact therewith, enhances the effect of the N-nitroso-oxime compound. However it is thought that the complex formed between the metallic contaminants of the photographic material and the N-nitroso-oxime is extracted from the silver halide emulsion layer into the oil-former dispersion. It is possible that the complex formed between N-nitroso-oximes and metal contaminants has some effect on latent image stability and in the production of spot marks, but a much reduced effect compared with the metal contaminants per se, so that when this complex is completely removed from the silver halide phase an even greater improvement in latent image stability and reduction in spot marks is obtained. Complexes formed between the N-nitroso-oximes of formula I and copper or iron are more soluble in the oil-formers than in the gelatin or other binder phase of the emulsion and thus the complex is preferentially extracted from the silver halide phase into the oil-former phase of the layers.
The presence of iron and coper contamination has been stressed because most photographic silver halide emul' sions contain in the region of parts per million of iron and in the region of 20 parts per million of copper.
The presence of an oil-former in the photographic material which is able to extract the N-nitroso-oxime-metal complexes from the aqueous phase of the layers of the photographic material is advantageous even when the N nitroso-oxime is added to the material for the purpose of lessening the spot formation due to gross metallic contamination. This is illustrated in Example 5 which follows.
Therefore, according to another embodiment of the present invention there is provided photographic material which comprises a support base having coated thereon one or more layers, at least one of which is a photographic layer, there being present in at least one layer of the material a dispersion of an oil-former and there being present in the same layer or in a layer in operative contact therewith a N-nitroso-oxime of formula I.
In a preferred embodiment of this aspect of the present invention there is provided photographic material which comprises a support base carrying thereon a silver halide emulsion layer having dispersed therein a water-insoluble organic-solvent-soluble high boiling point oil-former, there being present in the silver halide emulsion layer or in a layer in operative contact therewith a N-nitrosooxime compound of formula I.
Preferably in this aspect of the invention the N-nitrosooxime is present in the silver halide emulsion layer, the preferred oil-former is dibutyl phthalate and the preferred N-nitroso-oxime is the compound of formula II.
It has been found that the N-nitroso-oxime compounds of formula I act more eiiiciently in preventing spot marks due to copper contamination when there is present in the layer of the photographic material which contains the N- nitroso-oxime compound, or in a layer in operative contact therewith, salicylaldoxime. Some increased effect is apparent also in the prevention of spots due to iron contamination.
Therefore, according to yet another embodiment of the present invention there is provided photographic material 'which comprises a support base having coated thereon one or more layers, at least one of which is a photographic layer, there being present in at least one layer of the material salicylaldoxime and there being present in the same layer or in a layer in operative contact therewith a N-nitroso-oxime of formula I.
In a preferred embodiment of this aspect of the present invention there is provided photographic material which comprises a support base carrying thereon a silver halide emulsion layer which comprises salicylaldoxime, there being present in the silver halide emulsion layer or in a layer in operative contact therewith a N-nitrosooxime compound of formula I.
Preferably the amount of salicylaldoxime present in the silver halide emulsion is from 0.01-10 g. per mole of silver halide in the emulsion.
The N-nitroso-oxime compounds of formula I may be added to photographic emulsions at any stage in the emulsion making process provided they remain present in the finished emulsion.
The silver halide emulsion to which the N-nitrosooxime compounds of formula I may be added may comprise any of the normal silver halides, for example, silver chloride, silver bromide or silver iodobromide. The emulsion binder is preferably gelatin but may comprise other polymeric substances for example polyvinyl alcohol, polyvinyl pyrrolidone, ethyl cellulose or an alginate, either alone or in admixture with the gelatin.
The silver halide emulsion to which the N-nitrosooxime compounds of formula I may be added may contain any of the usual sulphur sensitizers for example thiourea or thiosulphate and may in addition be sensitized with a nobel metal, for example gold. Furthermore it may comprise polyethylene oxide sensitizers and the usual tetraazindene stabilizers and may contain further stabilizers, for example cadmium or mercury salts. The emulsion may also contain development anti-foggants.
The presence of color couplers in the silver halide emulsion does not appear to interfere in any way with the action of the N-nitroso-oxime compounds of formula I in reducing the tendency of the photographic material to exhibit latent image instability and the formation of spot marks.
The following Examples will serve to illustrate the invention.
EXAMPLE 1 A slow fine grain iodobromide emulsion was prepared, in gelatin solution, having 3.2 mole percent of silver iodide, the pH of the emulsion being adjusted to 6.0 and the pAg of the emulsion being adjusted to 8.4. This emulsion was digested at an elevated temperature in the presence of sodium thiosulphate and a gold salt to maximum sensitivity. The emulsion was then stabilized by the addition of a tetraazaindene compound and cooled. A wetting agent was then added to the emulsion, which was reheated and coated onto film strips. This was the control emulsion A.
Similar emulsions B and C were prepared and coated except that in the case of B, 5 mols of a 1% aqueous solution of the ammonium salt of N-nitroso-N-phenylhydroxylamine (the compound of formula II) was added per mole of silver halide in the emulsion to the emulsion immediately prior to coating the emulsion. In the case of emulsion C, 7 g. of a gelatin dispersion of dibutyl phthalate per mole of silver halide was added to the emulsion after digestion and then 5 moles of a 1% aqueous solution of the ammonium salt of N-nitroso-N- phenylhydroxylamine per mole of silver halide in the emulsion was added to the emulsion immediately prior to coating the emulsion.
The gelatin dispersion of dibutyl phthalate was made by adding 5% of dibutyl phthalate to 129 g. of gelatin dissolved to form a concentrated aqueous solution, ml. of Perminal BX, a naphthalene sulphonate based dispersing agent marketed by Imperial Chemical Industries Limited, was then added to the mixture and the mixture was mechanically stirred in order to disperse the dibutyl phthalate in the gelatin solution.
In each test one strip of the control emulsion and the strips of the test emulsions were all exposed to flash through a stepwedge and then incubated for 7 days at 69% RH. at 43 C. such conditions being chosen to accelerate any tendency to latent image regression.
All the strips were then processed for 8 minutes at C. in a metol/hydroquinone-based developers (ID-2 marketed by Ilford Limited). The relative log speed measured at a density of 0.1 above fog of all the strips was then determined and compared with the relative log speed at 0.1 above fog of identical strips of emulsions A, B and C which after coating were stored for seven days at room temperature, exposed through a stepwedge and then at once processed as above.
In the case of emulsion A there was a speed loss of 0.25 log E units in the sample which had been incubated for seven days after exposure compared with the sample which had been developed at once after exposure.
In the case of emulsion B there was a speed loss of 0.18 log E units in the sample which had been incubated for seven days after exposure compared with the sample which had been developed at once after exposure.
In the case of emulsion C there was a speed loss of 0.12 log E units in the sample which had been incubated for seven days after exposure compared with the sample which had been developed at once after exposure.
This test shows that the presence of the compound of formula II in the emulsion reduces the latent image regression of the emulsion after exposure. Also when the compound of formula II and a dispersion of dibutyl phthalate are present simultaneously in the emulsion the latent image regression of the emulsion after exposure is further reduced.
EXAMPLE 2 Three samples A, B and C of a fast coarse-grained iodobromide emulsion were prepared as in Example 1. Samples of these emulsions were exposed, incubated and processed as in Example 1.
Three sets of test were carried out. In tests 1, 2 and 3 the three emulsion samples A, B and C which had been incubated for seven days after exposure were compared for speed loss with the three same emulsion samples which had been exposed and processed at one. In test 1 the speed loss of the emulsion at 0.1 above fog was determined. In test 2 the speed loss or gain at 1.5 above fog was determined. In test 3 the development time of the emulsions was lowered to 3 minutes and the speed loss or gain at 0.1 above fog was determined. In test 4 the development time of the emulsions was also 3 minutes and the speed loss or gain at 1.5 above fog was determined.
Table 1 below shows the results obtained.
TABLE 1 Test (log E units) Emulsion 1 2 3 4 EXAMPLE 3 A slow fine grain iodobromide emulsion was prepared and coated exactly as in Example 1. This was the control emulsion A.
Similar emulsions D and B were prepared and coated except that in the case of D, 10 mols of a 1% aqueous solution of the compound of formula II was added per mole of silver halide. In the case of emulsion E 7 g. of a dibutyl phthalate dispersion (prepared as in Example 1) was added to the emulsion after digestion and then 10 mols of a 1% aqueous solution of the compound of formula III was added per mole of silver halide.
Strips of these three emulsions were tested as set forth in Example 1.
In the case of emulsion A there was a speed loss of 0.20 log E units in the sample which had been incubated for seven days after exposure compared with the sample which had been developed at once after exposure.
In the case of emulsion D there was a speed loss of 0.16 log E units in the sample which had been incubated for seven days after exposure compared with the sample which had been developed at once after exposure.
In the case of emulsion B there was a speed loss of 0.14 log E units in the sample which had been incubated for seven days after exposure compared with the sample which had been developed at once after exposure.
Comparably with Example 1 this test shows that the presence of the compound of formula -III in the emulsion reduces the latent image regression of the emulsion after exposure. Also when the compound of formula III and a dispersion of dibutyl phthalate are present simultaneously in the emulsion the latent image regression of the emulsion after exposure is further reduced.
9 EXAMPLE 4 A slow fine grain iodobromide emulsion was prepared and coated as in Example 1. This was the control emulsion A.
Similar emulsions F and G were prepared and coated except that in the case of emulsion F 160 mols of 1% aqueous solution of the compound of formula IV was added per mole of silver halide. In the case of emulsion G 7 g. of a dibutyl phthalate dispersion (prepared as in Example 1) was added to the emulsion after digestion and then 160 mols of a 1% aqueous solution of the compound of formula IV was added per mole of silver halide.
Strips of these three emulsions were tested as set forth in Example 1 In the case of emulsion A there was a speed loss of 0.36 log E units in the sample which had been incubated for seven days after exposure compared with the sample which had been developed at once after exposure.
In the case of emulsion F there was a speed loss of 0.30 log E units in the sample which had been incubated for seven days after exposure compared with the sample which had been developed at once after exposure.
In the case of emulsion G there was a speed loss of 0.24 log E units in the sample which had been incubated for seven days after exposure compared with the sample which had been developed at once after exposure. comparably with Examples 1 and 2 this test shows that the presence of the compound of formula IV in the emulsion reduces the latent image regression of the emulsion after exposure. Also when a compound of formula IV and a dispersion of dibutyl phthalate are present simultaneously in the emulsion the latent image regression of the emulsion after exposure is further reduced.
EXAMPLE 5 6.5. This material is referred to as sample M. A similar.
sample was prepared (referred to as N) except that there was added to 1 kg. of the silver halide emulsion just prior to coating 100 ml. of a 1% ethanolic solution of the compound of formula H. A third sample P was prepared; in this sample there was added to the silver halide emulsion prior to coating, in addition to the compound of formula II, 100 ml. of a gelatin dispersion containing 30% dibutyl phthalate.
A fourth sample Q was prepared as M except that there was added to 1 kg. of the silver halide emulsion just prior to coating 100 ml. of a 1% ethanolic solution of the compound of formula III. A fifth sample R was prepared and in this sample there was added to 1 kg. of the silver halide emulsion prior to coating in addition to the compound of formula HI, 100 ml. of a gelatin dispersion containing 30% dibutyl phthalate. A sixth sample S was prepared as sample M except that there was added to 1 kg. of the silver halide emulsion just prior to coating 100 ml. of a 1% ethanolic solution of the compound of formula VII. A seventh sample T was also prepared and in this sample there was added to 1 kg. of the silver halide emulsion just prior to coating 100 ml. of a gelatin dispersion containing 30% dibutyl phthalate in addition to the compound of formula VII.
Samples M, N, -P, Q, R, S and T were exposed to light and developed for 4 minutes in a Phenidone/hydroquinone based developer. On inspection, after drying, sample M was found to have numerous light patches centered on the copper particles. Samples N, Q and S were found to have some light patches centered on the copper particles, but
very much fewer than in sample M. However, in samples P, R and T there were almost no light patches centered on the copper particles.
EXAMPLE 6 This example illustrates the effect caused by iron and rust on the silver halide emulsion and illustrates the improvement obtained by the additives used in the present invention.
A silver iodobromide emulsion having a pH of 6.5 was applied to a gelatin layer which contained very fine iron powder and rust coated on a film support (sample VIII). A similar sample Y was prepared except that there was added to 1 kg. of the silver iodobromide emulsion just prior to coating 75 mols of a 1% aqueous solution of the compound of formula IH. Similar samples U, V, W and Z were prepared containing respectively 75 mols of a 1% solution of the compound of formulae III, IV, V and VIII. Samples X, Y, Z, U, V and NV were then light exposed and developed for 4 minutes in a l-phenyl-3- pyrazolidone/hydroquinone based developer. In sample VIII there were found to be a large number of sensitized black spots which were due to (metal ions from) the iron and rust coming into contact with the silver halide emulsion and causing sensitized marks. However, in samples Y, Z, U, V and W the number of sensitized black marks was considerably reduced compared with sample VHI.
EXAMPLE 7 A silver iodobromide emulsion having a pH of 6.5 was applied to a gelatin layer which contained very fine copper particles coated onto a film support (sample A). Similar samples were prepared except that there were added to the silver iodobromide emulsion 6 mols of a 20% ethanolic solution of salicylaldoxime per mole of silver halide (sample B) mols of a 2% aqueous solution of the ammonium salt of N-nitrosoN-phenylhydroxylamine (the compound of formula II) per mole of silver halide (sample C) and finally salicylaldoxime and the ammonium salt of N-nitroso-N-phenylhydroxylamine ta gether in the above quantities (sample D). Samples A, B, C and D were then light exposed and developed for 4 minutes in a 1-phenyl-3-pyrazolidone/hydroquinonebased developer. In sample A there were numerous desensitized (white) spots centered on the copper particles. In sample B, these desensitized spots were slightly reduced in size, while in sample C both their numbers and their intensities were greatly reduced. In sample D no desensitized areas were observed.
What we claim is:
1. A photographic material which comprises a support base having coated thereon one or more layers, at least one of which is a photosensitive silver halide emulsion layer, there being present in at least one layer of the material a water-soluble N-nitroso-oxime of the formula wherein A represents a phenyl or naphth-lor -2-yl radical or a phenyl or naphth-lor -2-yl radical substituted by one or two members selected from hydrogen, halogen, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms and aralkyl and R is a cation.
2. A photographic material according to claim 1 which comprises a compound of formula I defined in claim 1 wherein A is a phenyl-, naphth-l-yl-, 2,3- or 3,4-dimethylphen-1-yl-, 2- or 4-methyl-pheny-l-yl-, 4-chlorophen-l-yl-, Z-chloro-S-methyl-phen-l-yl-, 2- or 4-ethylpheny-l-ylor 4-(fl-hydroxyethyl)-phen-l-yl-radical and R is the NH.; group as the water-soluble N-nitroso-oxime.
3. A photographic material according to claim 1 which comprises a compound of formula I defined in claim 1 wherein A is phenyl and R is the NH., group as the water-soluble N-nitroso-oxime.
4. A photographic material according to claim 1 which comprises a compound of formula I defined in claim 1 wherein A is naphth-l-yl and R is the NH.; group as the water-soluble N-nitroso-oxime.
5. A photographic material according to claim 1 which comprises at least one layer containing dispersed therein a water-insoluble organic-solvent-soluble high 'boiling point oil-former, selected from the group consisting of a high boiling petroleum fraction, dibutyl phthalate, 1,2- di-methoxybenzene, verotrole, diphenyl, diphenylether, N,N-dibutyllauramide, 2,4 di-n-amylphenyl, tricresylphosphate, benzophenone and ethyloleate and a watersoluble N-nitroso-oxime of the formula I A-N-O-R N L .0
wherein A and R have the meanings given in claim 1 which oxime is contained in the same layer or in a layer adjacent to the layer containing the oil-former.
6. A photographic material according to claim 5 which comprises a compound of the formula I defined in claim 5 wherein A is phenyl and R is the -NH.; group as the water-soluble N-nitroso-oxime.
7. A photographic material according to claim 5 which comprises a compound of the formula I defined in claim 5 wherein A is naphth-l-yl and R is the -NH.; group as the water-soluble N-nitroso-oxime.
8. A photographic material according to claim 1 wherein salicylaldoxime is contained in the same layer as the water-soluble N-nitroso-oxime or in a layer adjacent to the said layer.
9. A photographic material according to claim 1 which comprises a silver halide emulsion layer as the photosensitive layer and a water-soluble N-nitroso-oxime of formula I wherein A and R have the meanings given in claim 1 which oxime is contained in said silver halide emulsion layer or in a layer adjacent to said layer.
10. A photographic material according to claim 9 which comprises a compound of formula I defined in claim 9 wherein A is phenyl and R is the ---NH.; group.
'11. A photographic material according to claim 9 which comprises a compound of formula I defined in claim 9 wherein A is naphth-l-yl and R is the NH; group.
12. A photographic material according to claim 9 wherein the water-soluble N-nitroso-oxime is present in an amount of from 0.01 to 10 g. per mole of silver halide in the silver halide emulsion layer or in a layer adjacent to said layer.
13. A photographic material, according to claim 5 wherein the oil-former is dibutyl phthalate.
14. A photographic material according to claim 9 wherein 'both the water-soluble N-nitroso-oxime of the formula I AN0R wherein A and R have the meaning given in claim 9 and salicylaldoxime are present in a silver halide emulsion layer.
15. A photographic material according to claim 14 wherein the salicylaldoxime is present in an amount of from 0.01 to 10 g. per mole of silver halide, in the silver halide emulsion layer.
16. A photographic material according to claim 15 which comprises a compound of formula I wherein A is phenyl and R is the -NH group as water-soluble N- nitroso-oxime.
References Cited UNITED STATES PATENTS 2,675,314 4/1954 Vittum 96109 3,148,066 9/1964 I-Iolstead 96-109 3,189,454 6/1965 Luckey 9661 R 3,393,072 7/1968 Ohi 96109 3,271,143 9/1966 Sorensen 96--1'1.7
NORMAN G. TORCHIN, Primary Examiner A. T. SURO PICO, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (1)
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GB395771 | 1971-02-04 |
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US3813249A true US3813249A (en) | 1974-05-28 |
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US00222663A Expired - Lifetime US3813249A (en) | 1971-02-04 | 1972-02-01 | Light sensitive photographic material |
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US (1) | US3813249A (en) |
BE (1) | BE778909A (en) |
DE (1) | DE2204057A1 (en) |
FR (1) | FR2124446B1 (en) |
GB (1) | GB1322812A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996036326A1 (en) * | 1995-05-15 | 1996-11-21 | Board Of Regents, The University Of Texas System | N-nitroso-n-substituted hydroxylamines as nitric oxide donors |
US6103275A (en) * | 1998-06-10 | 2000-08-15 | Nitric Oxide Solutions | Systems and methods for topical treatment with nitric oxide |
-
1971
- 1971-02-04 GB GB395771*[A patent/GB1322812A/en not_active Expired
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1972
- 1972-01-28 DE DE19722204057 patent/DE2204057A1/en active Pending
- 1972-02-01 US US00222663A patent/US3813249A/en not_active Expired - Lifetime
- 1972-02-03 FR FR7203663A patent/FR2124446B1/fr not_active Expired
- 1972-02-03 BE BE778909A patent/BE778909A/en unknown
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996036326A1 (en) * | 1995-05-15 | 1996-11-21 | Board Of Regents, The University Of Texas System | N-nitroso-n-substituted hydroxylamines as nitric oxide donors |
US5698738A (en) * | 1995-05-15 | 1997-12-16 | Board Of Regents, The University Of Texas System | N-nitroso-N-substituted hydroxylamines as nitric oxide donors |
US6103275A (en) * | 1998-06-10 | 2000-08-15 | Nitric Oxide Solutions | Systems and methods for topical treatment with nitric oxide |
Also Published As
Publication number | Publication date |
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FR2124446B1 (en) | 1974-08-30 |
DE2204057A1 (en) | 1972-08-17 |
FR2124446A1 (en) | 1972-09-22 |
BE778909A (en) | 1972-08-03 |
GB1322812A (en) | 1973-07-11 |
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